U.S. patent application number 14/000440 was filed with the patent office on 2013-12-12 for novel heterocyclic compound, method for producing intermediate therefor, and use thereof.
This patent application is currently assigned to NIPPON KAYAKU KABUSHIKI KAISHA. The applicant listed for this patent is Eisei Kanoh, Hirokazu Kuwabara, Kazuki Niimi, Yuichi Sadamitsu, Kazuo Takimiya. Invention is credited to Eisei Kanoh, Hirokazu Kuwabara, Kazuki Niimi, Yuichi Sadamitsu, Kazuo Takimiya.
Application Number | 20130330876 14/000440 |
Document ID | / |
Family ID | 46721008 |
Filed Date | 2013-12-12 |
United States Patent
Application |
20130330876 |
Kind Code |
A1 |
Takimiya; Kazuo ; et
al. |
December 12, 2013 |
Novel Heterocyclic Compound, Method For Producing Intermediate
Therefor, And Use Thereof
Abstract
Provided are a novel heterocyclic compound represented by
formula (1), and a field-effect transistor having a semiconductor
layer comprising the aforementioned compound. Also provided is a
method for producing an intermediate enabling the production of the
aforementioned novel heterocyclic compound. (In the formula,
R.sup.1 and R.sup.2 represent a hydrogen atom, a C.sub.2-16 alkyl
group or an aryl group. However, when R.sup.1 each independently
represents a C.sub.2-16 alkyl group or an aryl group, R.sup.2
represents a hydrogen atom or each independently represents an aryl
group; and when R.sup.1 represents a hydrogen atom, R.sup.2 each
independently represents an aryl group.) ##STR00001##
Inventors: |
Takimiya; Kazuo;
(Higashihiroshima, JP) ; Niimi; Kazuki;
(Higashihiroshima, JP) ; Kuwabara; Hirokazu;
(Tokyo, JP) ; Sadamitsu; Yuichi; (Tokyo, JP)
; Kanoh; Eisei; (Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Takimiya; Kazuo
Niimi; Kazuki
Kuwabara; Hirokazu
Sadamitsu; Yuichi
Kanoh; Eisei |
Higashihiroshima
Higashihiroshima
Tokyo
Tokyo
Tokyo |
|
JP
JP
JP
JP
JP |
|
|
Assignee: |
NIPPON KAYAKU KABUSHIKI
KAISHA
Tokyo
JP
HIROSHIMA UNIVERSITY
Hiroshima
JP
|
Family ID: |
46721008 |
Appl. No.: |
14/000440 |
Filed: |
February 24, 2012 |
PCT Filed: |
February 24, 2012 |
PCT NO: |
PCT/JP2012/054604 |
371 Date: |
August 20, 2013 |
Current U.S.
Class: |
438/99 ; 549/41;
568/52; 568/57 |
Current CPC
Class: |
C07C 319/20 20130101;
H01L 51/0558 20130101; C09K 11/06 20130101; C09K 2211/1092
20130101; C07C 319/20 20130101; C09B 57/00 20130101; C09K 2211/1011
20130101; C07C 321/28 20130101; C07D 495/04 20130101; H01L 51/0074
20130101 |
Class at
Publication: |
438/99 ; 568/52;
568/57; 549/41 |
International
Class: |
H01L 51/00 20060101
H01L051/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 25, 2011 |
JP |
2011-039403 |
Claims
1. A heterocyclic compound represented by the following formula
(1): ##STR00030## (wherein R.sup.2 and R.sup.2 each represent one
of a hydrogen atom, a C2-C16 alkyl group, and an aryl group; when
R.sup.2 each independently represents a C2-C16 alkyl group or an
aryl group, R.sup.2 each represents a hydrogen atom or R.sup.2 each
independently represents an aryl group; and when R.sup.2 represents
a hydrogen atom, R.sup.2 each independently represents an aryl
group).
2. The heterocyclic compound according to claim 1, wherein in the
formula (1), R.sup.2 each independently is a linear C5-C12 alkyl
group, and R.sup.2 each is a hydrogen atom.
3. The heterocyclic compound according to claim 1, wherein in the
formula (1), R.sup.2 each independently is an aryl group having one
of a phenyl structure, a naphthyl structure, and a biphenyl
structure, and R.sup.2 each is a hydrogen atom.
4. The heterocyclic compound according to claim 1, wherein in the
formula (1), R.sup.1 is a hydrogen atom, and R.sup.2 each
independently is an aryl group having one of a phenyl structure, a
naphthyl structure, and a biphenyl structure.
5. The heterocyclic compound according to claim 3, wherein in the
formula (1), R.sup.1 each independently is an aryl group selected
from the group consisting of a phenyl group, a 4-alkylphenyl group,
a 1-naphthyl group, and a biphenyl group, and R.sup.2 is a hydrogen
atom.
6. The heterocyclic compound according to claim 4, wherein in the
formula (1), R.sup.1 each is a hydrogen atom, and R.sup.2 each
independently is an aryl group selected from the group consisting
of a phenyl group, a 4-alkylphenyl group, a 1-naphthyl group, and a
biphenyl group.
7. A method for producing an intermediate compound represented by a
formula (4) in production of a heterocyclic compound represented by
a formula (2), the method comprising reacting a compound
represented by a formula (3) with dimethyl disulfide: ##STR00031##
(wherein R.sup.3 represents a substituent); ##STR00032## (wherein
R.sup.3 and R.sup.4 represent a substituent).
8. A method for producing an intermediate compound represented by a
formula (6) in production of a heterocyclic compound represented by
a formula (2), the method comprising reacting a compound
represented by a formula (4) with a tin compound represented by a
formula (5): ##STR00033## (wherein R.sup.3, R.sup.4, and R.sup.5
represent a substituent).
9. An organic semiconductor material comprising one or two or more
heterocyclic compounds represented by the formula (1) according to
claim 1.
10. An ink for creating a semiconductor device, comprising one or
two or more heterocyclic compounds represented by the formula (1)
according to claim 1.
11. An organic thin film comprising one or two or more heterocyclic
compounds represented by the formula (1) according to claim 1.
12. A method for producing an organic thin film, wherein the
organic thin film according to claim 11 is formed by a deposition
method.
13. A method for producing an organic thin film, which comprises
applying the ink according to claim 10.
14. A field effect transistor comprising an organic thin film
according to claim 11.
15. The field effect transistor according to claim 14, wherein the
field effect transistor is a bottom contact type.
16. The field effect transistor according to claim 14, wherein the
field effect transistor is a top contact type.
17. A method for producing a field effect transistor, comprising
the step of forming an organic thin film on a substrate by the
method according to claim 12.
18. A method for producing a field effect transistor, comprising
the step of forming an organic thin film on a substrate by the
method according to claim 13.
Description
TECHNICAL FIELD
[0001] The present invention relates to a novel heterocyclic
compound, a novel method for producing an intermediate enabling
synthesis of the compound, and use of the compound. More
specifically, the present invention relates to a novel
[1]benzothieno[3,2-b][1]benzothiophene derivative usable as an
organic semiconductor or the like, and an effective method for
producing an intermediate enabling synthesis of the derivative. The
present invention also relates to a field effect transistor using
the compound.
BACKGROUND ART
[0002] The field effect transistor is typically an element having a
semiconductor layer (semiconductor film), a source electrode, a
drain electrode, and a gate electrode for each of these electrodes
provided with an insulator layer being interposed therebetween, and
the like on a substrate. The field effect transistor is used as a
logic circuit element in integrated circuits, and widely used as a
switching element and the like. The semiconductor layer is
typically formed of a semiconductor material. The field effect
transistor at present is formed using an inorganic semiconductor
material, which is mainly silicon. A thin film transistor having a
semiconductor layer created on a substrate such as glass using
amorphous silicon in particular is used for displays or the like.
In use of such an inorganic semiconductor material, the workpiece
needs to be treated at a high temperature or in vacuum during
production of the field effect transistor. Therefore, large
investment in facility and a large amount of energy during
production are necessary, leading to very high production cost.
Moreover, because these components are exposed to a high
temperature during production of the field effect transistor, a
material having insufficient heat resistance such as films and
plastics is difficult to use as the substrate. A flexible material
that can be bent, for example, is difficult to use as the
substrate. Thus, the application area of the field effect
transistor is limited.
[0003] Meanwhile, field effect transistors using an organic
semiconductor material have been studied and developed actively.
Use of the organic material can eliminate the treatment at a high
temperature, and allow the process at a low temperature, leading to
variety of substrate materials that can be used.
[0004] As a result, recently, a field effect transistor more
flexible, lighter, and more difficult to break than the
conventional field effect transistor has been able to be created.
In a step of creating the field effect transistor, a method such as
application of a solution prepared by dissolving a semiconductor
material and printing of the solution by inkjet may be used, and
can produce a field effect transistor having a large area at low
cost. A variety of compounds for the organic semiconductor material
can be selected, and utilization of the properties of the compound
and development of the functions that do not exist before are
expected.
[0005] As an example in which an organic compound is used as the
semiconductor material, a variety of organic compounds have been
studied. For example, organic materials using pentacene, thiophene,
or an oligomer or polymer thereof are already known as a material
having hole transport properties (see Patent Literature 1 and
Patent Literature 2). Pentacene is an acene aromatic hydrocarbon
including 5 benzene rings linearly condensed. It is reported that
the field effect transistor using pentacene as the semiconductor
material exhibits mobility of charges (carrier mobility) equal to
that of amorphous silicon that is used in practice. The field
effect transistor using pentacene, however, deteriorates due to an
environment, and has problems with stability. The field effect
transistor using a thiophene compound also has the same problems,
and it is hard to say that these materials have high practicality.
Dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) being stable
in the air and having high carrier mobility has been developed
recently, and received attention (see Patent Literature 3 and Non
Patent Literature 1). Unfortunately, even these compounds need to
have higher carrier mobility for use in applications of displays
such as organic ELs. Development of a high quality and high
performance organic semiconductor material is demanded from the
viewpoint of durability.
[0006] Citation list on a DNTT derivative having a substituent
includes Patent Literatures 3, 4, and 5. Specific examples of the
substituent include a methyl group, a hexyl group, an alkoxyl
group, and a substituted ethynyl group. The substituents in the
DNTT derivative described as Examples are only a methyl group and a
substituted ethynyl group. These groups exhibit only semiconductor
properties equal to or less than those of DNTT having no
substituent.
[0007] Later, Patent Literature 6 describes
dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene in Formula 1 (Alkyl
DNTT, wherein Alkyl represents a C5 to C16 alkyl group) wherein
dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene has properties more
excellent than those of the conventional organic semiconductor
material in the respect above. Patent Literature 6 shows that the
field effect transistor element using this compound is not
influenced by the states of the substrate and insulation film
during creation of the element (or irrespective of whether a
substrate is treated or not), and has extremely improved
semiconductor properties; and that the effect is remarkably
enhanced by performing a heat treatment during creation of the
element.
##STR00002##
[0008] As described above, these DNTT derivatives useful for the
organic semiconductors have been developed, but the conventional
production methods have limitation in a method for constructing
particularly a thienothiophene structure portion. Namely, a DNTT
having a substituent selectively in a position other than the
2,9-positions is difficult to produce, leading to delay of
development of a derivative of DNTT. The following three methods of
producing a DNTT derivative are mainly known. These will be
described below.
[0009] The first method is a method in which a derivative is
constructed using a starting material tetrabromothienothiophene
having a thienothiophene structure from the beginning (Patent
Literature 5). In this production method, unsubstituted
benzaldehyde causes no problem, but the method has a disadvantage
in which use of benzaldehyde having a substituent produces a
mixture of DNTT derivatives having substituents at various
positions.
##STR00003##
[0010] The second method is a method of producing a derivative from
an ethylene derivative. Most of DNTT derivatives have been
synthesized by this method (Non Patent Literature 1, Patent
Literature 3, Patent Literature 6, Patent Literature 7, and Patent
Literature 8).
[0011] For example, Patent Literature 6 discloses that according to
the known methods disclosed in Patent Literature 3 and Non Patent
Literature 1,2-alkyl-7-methylthio-6-naphthoaldehyde (B) is obtained
from 2-alkyl-6-naphthoaldehyde (A), and condensed to obtain
1,2-bis(2-alkyl-7-methylthio-6-naphthyl)ethylene (C). Patent
Literature 6 also discloses that
1,2-bis(2-alkyl-7-methylthio-6-naphthyl)ethylene (C) can be further
ring closed to obtain a target compound
2,9-dialkyldinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene
(2,9-dialkyl DNTT).
[0012] Namely, in Patent Literature 6, the compound (B) is obtained
by reacting dimethyl sulfide with the compound (A), and the
condensate (C) is obtained by McMurry coupling. Further, the target
DNTT derivative is obtained by making a ring close reaction in
chloroform using the condensate (C) and iodine. Unlike the above
first method, the second method is a production method that can
produce only a DNTT derivative having a substituent in the target
position.
##STR00004##
[0013] The disadvantage of this synthetic route is that the
selectivity of the SMethylation reaction of the compound (A) is
approximately 60%, namely, SMethylation in naphthalene at the
7-position as desired occurs only approximately 60%. In
approximately 30% of the compound (A), SMethylation undesirably
occurs at the 5-position, and approximately 10% of the raw material
is recovered. As a result, the compound (B) is extremely difficult
to separate and refine.
[0014] From above, this method has disadvantages in that the
Alkyl-substituted compound (B) cannot be separated by
recrystallization that is a method at industrially low cost or the
like, needs to be subjected to column refining using an adsorbent
(such as silica gel) accompanied by large investment in facility,
and cannot be produced at low cost. When the substituent is an aryl
group, the separation and the production are more difficult.
Additionally, the reaction shown in the reaction formula (2) cannot
produce the DNTT having a substituent at 3,10-positions because of
limitation in the raw material. This method has such problems, but
the method using the compound (B) as the raw material have to be
selected in the related art to generate the compound (C)
efficiently.
[0015] As above, the compound (C) is important in development of
the DNTT derivative, but difficulties in synthesis and separation
of the compound (B) as the raw material for the DNTT derivative at
industrially low cost are known. These difficulties lead to delay
of development of the DNTT having a substituent. For this reason,
it is easily presumed that if development of an intermediate
compound for producing the compound (C) progresses, following this,
development of a derivative of the DNTT having a substituent
significantly progresses. Development of such a method for
producing an intermediate has been required.
[0016] The third method is a typical synthesis method using an
acetylene derivative (E) (Patent Literature 7). In this synthetic
method, it cannot be said yet that an industrial method for
producing a Br body (D) as a raw material is established, and a
problem of the method is the difficulties in synthesis of an
acetylene derivative (E) (Patent Literature 7, Patent Literature
9). Another problem of the method is that cyclization reaction of
an acetylene derivative with iodine usually has a low yield (in
Patent Literature 7, a yield of approximately 10% to 40%).
##STR00005##
CITATION LIST
Patent Literature
[0017] [Patent Literature 1] JP 2001-94107 A [0018] [Patent
Literature 2] JP 06-177380 A [0019] [Patent Literature 3]
WO2008/050726 [0020] [Patent Literature 4] JP 2008-10541 A [0021]
[Patent Literature 5] KR2008100982 [0022] [Patent Literature 6]
WO2010/098372 [0023] [Patent Literature 7] JP 2009-196975 A [0024]
[Patent Literature 8] WO2009/009790 [0025] [Patent Literature 9] JP
2010-258214 A
Non Patent Literature
[0025] [0026] [Non Patent Literature 1] J. Am. Chem. Soc., Vol.
129, 2224-2225 (2007)
SUMMARY OF INVENTION
Technical Problem
[0027] An object of the present invention is to provide a novel
heterocyclic compound exhibiting high carrier mobility and having
practical properties as a semiconductor, a novel method for
producing an intermediate enabling synthesis of the compound, a
semiconductor material comprising the compound, and a field effect
transistor having an organic semiconductor thin film formed of the
compound, and a production method therefor.
Solution to Problem
[0028] As result of an extensive research to solve the problems
above, the present inventors succeeded in development of a novel
heterocyclic compound and a novel method for producing an
intermediate enabling synthesis of the compound. The present
inventors found out that the novel heterocyclic compound exhibits
high carrier mobility and has practical properties as a
semiconductor, and can provide a semiconductor material comprising
the compound, a field effect transistor having an organic
semiconductor thin film formed of the compound, and a production
method therefor. Thus, the present invention has been
completed.
[0029] Namely, one aspect of the present invention relates to:
[1] A heterocyclic compound represented by the following formula
(1):
##STR00006##
(wherein R.sup.1 and R.sup.2 each represent one of a hydrogen atom,
a C2-C16 alkyl group, and an aryl group; when R.sup.1 each
independently represents a C2-C16 alkyl group or an aryl group,
R.sup.2 each represents a hydrogen atom or R.sup.2 each
independently represents an aryl group; and when R.sup.1 represents
a hydrogen atom, R.sup.2 each independently represents an aryl
group). [2] The heterocyclic compound according to [1], wherein in
the formula (1), R.sup.1 each independently is a linear C5-C12
alkyl group, and R.sup.2 each is a hydrogen atom. [3] The
heterocyclic compound according to [1], wherein in the formula (1),
R.sup.1 each independently is an aryl group having one of a phenyl
structure, a naphthyl structure, and a biphenyl structure, and
R.sup.2 each is a hydrogen atom. [4] The heterocyclic compound
according to [1], wherein in the formula (1), R.sup.1 is a hydrogen
atom, and R.sup.2 each independently is an aryl group having one of
a phenyl structure, a naphthyl structure, and a biphenyl structure.
[5] The heterocyclic compound according to [3], wherein in the
formula (1), R.sup.1 each independently is an aryl group selected
from the group consisting of a phenyl group, a 4-alkylphenyl group,
a 1-naphthyl group, and a biphenyl group, and R.sup.2 is a hydrogen
atom. [6] The heterocyclic compound according to [4], wherein in
the formula (1), R.sup.1 each is a hydrogen atom, and R.sup.2 each
independently is an aryl group selected from the group consisting
of a phenyl group, a 4-alkylphenyl group, a 1-naphthyl group, and a
biphenyl group. [7] A method for producing an intermediate compound
represented by a formula (4) in production of a heterocyclic
compound represented by a formula (2), the method comprising
reacting a compound represented by a formula (3) with dimethyl
disulfide:
##STR00007##
(wherein R.sup.3 represents a substituent);
##STR00008##
(wherein R.sup.3 and R.sup.4 represent a substituent). [8] A method
for producing an intermediate compound represented by a formula (6)
in production of a heterocyclic compound represented by a formula
(2), the method comprising reacting a compound represented by a
formula (4) with a tin compound represented by a formula (5):
##STR00009##
(wherein R.sup.3, R.sup.4, and R.sup.5 represent a substituent).
[9] An organic semiconductor material comprising one or two or more
heterocyclic compounds represented by the formula (1) according to
any one of [1] to [6]. [10] An ink for creating a semiconductor
device, comprising one or two or more heterocyclic compounds
represented by the formula (1) according to any one of [1] to [6].
[11] An organic thin film comprising one or two or more
heterocyclic compounds represented by the formula (1) according to
any one of [1] to [6]. [12] A method for producing an organic thin
film, wherein the organic thin film according to [11] is formed by
a deposition method. [13] A method for producing an organic thin
film, wherein the organic thin film according to [11] is formed by
applying the ink for creating a semiconductor device according to
[10]. [14] A field effect transistor comprising an organic thin
film according to [11]. [15] The field effect transistor according
to [14], wherein the field effect transistor is a bottom contact
type. [16] The field effect transistor according to [14], wherein
the field effect transistor is a top contact type. [17] A method
for producing a field effect transistor, comprising the step of
forming an organic thin film on a substrate by the method according
to [12] or [13], the organic thin film comprising one or two or
more heterocyclic compounds represented by the formula (1)
according to any one of [1] to [6].
Advantageous Effects of Invention
[0030] A field effect transistor including an organic thin film
comprising the novel heterocyclic compound represented by the
formula (1) as a semiconductor layer can provide a field effect
transistor having more excellent semiconductor properties such as
carrier mobility and durability than those of the transistor
including an organic thin film comprising the conventional organic
semiconductor material. Further, the novel method for producing a
key intermediate enabling production of these compounds in
industrial scale is a reaction having high selectivity. This novel
method also can produce the DNTT having an aryl group at the
2,9-positions and DNTT having a substituent at the 3,10-positions
that cannot be produced in the related art, and provide a
production method that can be used in industrial scale.
BRIEF DESCRIPTION OF DRAWINGS
[0031] FIG. 1 is a schematic view showing one embodiment of a field
effect transistor according to the present invention.
[0032] FIG. 2 is a schematic view showing steps for producing one
embodiment of the field effect transistor according to the present
invention.
[0033] FIG. 3 is a schematic view showing a field effect transistor
obtained in Comparative Example 1.
[0034] FIG. 4 shows light absorption spectrums of chloroform
solutions of DNTTs.
DESCRIPTION OF EMBODIMENTS
[0035] The present invention will be specifically described. The
present invention relates to an organic field effect transistor
using a specific organic compound as the semiconductor material. A
compound represented by the formula (1) is used as the
semiconductor material, and a semiconductor layer is formed of the
compound. First, the compound represented by formula (1) will be
described.
[0036] In the formula (1), R.sup.1 and R.sup.2 represent a hydrogen
atom, a C2-C16 alkyl group, or an aryl group. When R.sup.1 each
independently represents a C2-C16 alkyl group or an aryl group,
R.sup.2 represents a hydrogen atom or R.sup.2 represents each
independently an aryl group. When R.sup.1 is a hydrogen atom,
R.sup.2 each independently represents an aryl group.
[0037] Examples of the alkyl group for R.sup.1 include linear,
branched, or cyclic alkyl groups. The alkyl groups have carbon
atoms usually 2 to 16, preferably 4 to 14, more preferably 6 to
12.
[0038] Here, specific examples of linear alkyl groups include
ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,
n-pentadecyl, and n-hexadecyl.
[0039] Specific examples of branched alkyl groups include C3-C16
saturated branched alkyl groups such as i-propyl, i-butyl,
i-pentyl, i-hexyl, and i-decyl.
[0040] Specific examples of cyclic alkyl groups include C5-C16
cycloalkyl groups such as cyclohexyl, cyclopentyl, adamantyl, and
norbornyl.
[0041] The C2-C16 alkyl group is preferably saturated alkyl groups
rather than unsaturated alkyl groups, and preferably has no
substituent rather than has a substituent. Among these, C4-C14
saturated linear alkyl groups are preferable, C6-C12 saturated
linear alkyl groups are more preferable, and an n-hexyl group, an
n-octyl group, an n-decyl group, and an n-dodecyl group are still
more preferable.
[0042] The aryl group for R.sup.1 and R.sup.2 represents an
aromatic hydrocarbon group such as a phenyl group, a biphenyl
group, a pyrene group, a 2-methylphenyl group, a 3-methylphenyl
group, a 4-methylphenyl group, a 4-butylphenyl group, a
4-hexylphenyl group, a 4-octylphenyl group, a 4-decylphenyl group,
a xylyl group, a mesityl group, a cumenyl group, a benzyl group, a
phenylethyl group, an .alpha.-methylbenzyl group, a triphenylmethyl
group, a styryl group, a cinnamyl group, a biphenylyl group, a
1-naphthyl group, a 2-naphthyl group, an anthryl group, and a
phenanthryl group; and a heterocyclic group such as a 2-thienyl
group. These groups may have substituent(s) which may be the same
or different.
[0043] The aryl group is preferably an aryl group having a phenyl,
naphthyl, or biphenyl structure, and more preferably a phenyl
group, a 4-methylphenyl group, a 4-hexylphenyl group, a
4-octylphenyl group, a 4-decylphenyl group, a 1-naphthyl group, a
2-naphthyl group, and a biphenyl group.
[0044] When both of R.sup.1 represent a C2-C16 alkyl group or an
aryl group, R.sup.2 is a hydrogen atom or R.sup.2 each
independently represents an aryl group. When R.sup.1 is a hydrogen
atom, R.sup.2 each independently represents an aryl group. R.sup.1
may be the same or different, and R.sup.2 may be the same or
different. More preferably, R.sup.1 and R.sup.2 each independently
are the same. This means that preferably R.sup.1 on the left side
and R.sup.1 on the right side are the same and R.sup.2 on the left
side and R.sup.2 on the right side are the same, but R.sup.1 and
R.sup.2 do not need to be the same.
[0045] The compound represented by the formula (1) can be
synthesized by the method for producing a compound represented by
the formula (2) described later.
[0046] The method for refining the compound represented by the
formula (1) is not particularly limited, and a known method such as
recrystallization, column chromatography, and vacuum sublimation
refining can be used. These methods can be used in combination when
necessary.
[0047] Specific examples of the compound represented by the formula
(1) are shown in the Table 1. n indicates normal, i indicates iso,
s indicates secondary, t indicates tertiary, and cy indicates
cyclo. Ph indicates a phenyl group, Tolyl indicates a tolyl group,
PhPh indicates a biphenyl group, Nap indicates a naphthyl group,
and 2-thienyl indicates a 2-thiophene group. The blank indicates
hydrogen.
##STR00010##
TABLE-US-00001 TABLE 1 Compound No. R.sup.1 R.sup.2 (1)-01 Et
(1)-02 n-Pr (1)-03 i-Pr (1)-04 n-Bu (1)-05 i-Bu (1)-06 t-Bu (1)-07
n-C.sub.5H.sub.11 (1)-08 n-C.sub.6H.sub.13 (1)-09 n-C.sub.7H.sub.15
(1)-10 n-C.sub.8H.sub.17 (1)-11 n-C.sub.9H.sub.19 (1)-12
n-C.sub.10H.sub.21 (1)-13 n-C.sub.11H.sub.23 (1)-14
n-C.sub.12H.sub.25 (1)-15 n-C.sub.13H.sub.27 (1)-16
n-C.sub.14H.sub.29 (1)-17 n-C.sub.16H.sub.33 (1)-18
cy-C.sub.5H.sub.9 (1)-19 cy-C.sub.6H.sub.11 (1)-20
cy-C.sub.8H.sub.15 (1)-21 cy-C.sub.10H.sub.19 (1)-22 Ph (1)-23
4-Tolyl (1)-24 PhPh (1)-25 1-Nap (1)-26 2-Nap (1)-27 2-thienyl
(1)-28 4-HexylPh (1)-29 4-OctylPh (1)-30 4-DecylPh (1)-31 Ph (1)-32
4-Tolyl (1)-33 PhPh (1)-34 1-Nap (1)-35 2-Nap (1)-36 2-thienyl
(1)-37 4-HexylPh (1)-38 4-OctylPh (1)-39 4-DecylPh (1)-40 n-Bu Ph
(1)-41 n-C.sub.6H.sub.13 Ph (1)-42 n-C.sub.8H.sub.17 Ph (1)-43
n-C.sub.10H.sub.21 Ph (1)-44 n-C.sub.12H.sub.25 Ph (1)-45 Ph Ph
(1)-46 4-Tolyl Ph (1)-47 PhPh Ph (1)-48 1-Nap Ph (1)-49 2-thienyl
Ph (1)-50 Ph 4-Tolyl (1)-51 Ph PhPh (1)-52 n-C.sub.8H.sub.17
n-C.sub.8H.sub.17 (1)-53 n-C.sub.12H.sub.25 n-C.sub.12H.sub.25
[0048] Hereinafter, a method for producing the compound of the
present invention will be specifically described. The method for
producing the compound of the present invention is a novel
production method. This production method enables production at a
very high yield of not only the compound represented by the formula
(1) that is a novel compound, but also a known DNTT such as a DNTT
wherein R.sup.1 is a hydrogen atom and R.sup.2 is an alkyl group
(e.g. (C2-C16) alkyl group). The reaction formulas in the present
invention are shown as follows. Hereinafter, reaction formulas (4),
(5), and (6) will be described in order.
##STR00011##
[0049] First, the compound (3) that is a starting material for the
compound (2), and the compound (4) that is a product of the
reaction formula (4) will be described.
[0050] In the compound (3) and the compound (4), R.sup.3 represents
a substituent. Examples of the substituent include a hydrogen atom,
an alkyl group, an aryl group, an ether group, a thioether group,
an ester group, an acyl group, an amino group, a cyano group, and a
nitro group. These groups may have a substituent, and may be the
same or different.
[0051] Here, the alkyl group for R.sup.3 is a linear, branched, or
cyclic C1 to C16 alkyl group. The aryl group means the same as the
aryl group for R.sup.1 and R.sup.2 in the compound (1).
[0052] The ether group is an alkoxy group having an alkyl group
having 1 to 16 carbon atoms and bonded to an oxygen atom, or an
aryl group bonded to an oxygen atom (aryloxy group).
[0053] The thioether group is a thioalkoxy group having an alkyl
group having 1 to 16 carbon atoms and bonded to a sulfur atom, or
an aryl group bonded to a sulfur atom (arylthio group).
[0054] R.sup.3 is preferably C1-C16 saturated linear alkyl groups,
and aryl groups having a phenyl, naphthyl, or biphenyl structure.
R.sup.3 is more preferably C4-C14 saturated linear alkyl groups, a
phenyl group, a 4-methylphenyl group, and a biphenyl group.
[0055] In the compound (3) and the compound (4), R.sup.4 represents
a hydrogen atom; an alkyl group; an aryl group; an alkyl SO.sub.2
group; an aryl SO.sub.2 group; and an alkyl group, aryl group,
alkyl SO.sub.2 group or aryl SO.sub.2 group having one or more
fluorine atoms which one or more hydrogen atoms have been
substituted with.
[0056] Here, the alkyl group means the same as the alkyl group for
R.sup.3. The aryl group means the same as the aryl group for
R.sup.1 and R.sup.2. The alkyl SO.sub.2 group is an SO.sub.2 group
having the alkyl group as a substituent, and the aryl SO.sub.2
group is an SO.sub.2 group having the aryl group as a
substituent.
[0057] The alkyl group having one or more fluorine atoms which one
or more hydrogen atoms have been substituted with is an alkyl group
in which at least one hydrogen atom in the alkyl group is
substituted with a fluorine atom, and includes the alkyl group in
which all the hydrogen atoms are substituted with a fluorine atom
(hereinafter, these are generally referred to as a fluorinated
alkyl group as an abbreviation). Examples of preferable fluorinated
alkyl groups include an alkyl group in which all the hydrogen atoms
are substituted with a fluorine atom, and specifically include a
trifluoromethyl group and a perfluorohexyl group
(n-C.sub.6F.sub.13).
[0058] The aryl group having one or more fluorine atoms which one
or more hydrogen atoms have been substituted with is an aryl group
in which at least one hydrogen atom in the aryl group for the
substituent R.sup.3 is substituted with a fluorine atom, and
includes the aryl group in which all the hydrogen atoms are
substituted with a fluorine atom (hereinafter, these are generally
referred to as a fluorinated aryl group as an abbreviation).
Examples of preferable fluorinated aryl groups include a
4-trifluoromethylphenyl group (4-CF.sub.3C.sub.6H.sub.5), and a
pentafluorophenyl group (C.sub.6F.sub.5) that is an aryl group in
which all the hydrogen atoms are substituted with a fluorine
atom.
[0059] The alkyl SO.sub.2 group having one or more fluorine atoms
which one or more hydrogen atoms have been substituted with is a
fluorinated alkyl SO.sub.2 group. A preferable fluorinated alkyl
SO.sub.2 group is an alkyl SO.sub.2 group in which all the hydrogen
atoms are substituted with a fluorine atom. Examples thereof
include a trifluoromethyl SO.sub.2 group and a perfluorohexyl
SO.sub.2 group.
[0060] The aryl SO.sub.2 group having one or more fluorine atoms
which one or more hydrogen atoms have been substituted with is the
fluorinated aryl SO.sub.2 group. Examples of preferable fluorinated
aryl SO.sub.2 groups include a 4-fluorophenyl SO.sub.2 group, a
4-trifluoromethylphenyl SO.sub.2 group, and a pentafluorophenyl
SO.sub.2 group that is an aryl SO.sub.2 group in which all the
hydrogen atoms are substituted with fluorine atoms.
[0061] R.sup.4 is preferably a methyl group, a trifluoromethyl
group, a perfluorohexyl group, a 4-trifluoromethylphenyl group, a
pentafluorophenyl group that is an aryl group in which all the
hydrogen atoms are substituted with fluorine atoms, a
trifluoromethyl SO.sub.2 group, a perfluorohexyl SO.sub.2 group, a
4-trifluoromethylphenyl SO.sub.2 group, and a pentafluorophenyl
SO.sub.2 group that is an aryl group in which all the hydrogen
atoms are substituted with a fluorine atom. R.sup.4 is more
preferably a methyl group and a trifluoromethyl SO.sub.2 group.
[0062] Next, the reaction formula (4) will be described. The
compound represented by the following formula (3) as the starting
material is often available as commercially available products, and
can be easily synthesized by the method described in Examples.
[0063] Hereinafter, specific examples of the compound as the
starting raw material represented by the formula (3), namely the
compounds (3)-01 to (3)-85 will be shown, but the present invention
will not be limited to these. For convenience, R.sup.3 is written
as R.sup.31 and R.sup.32 below. The blank indicates a hydrogen
atom.
##STR00012##
TABLE-US-00002 TABLE 2 Compound No. R.sup.31 R.sup.32 R.sup.4
(3)-01 Et Me (3)-02 n-Pr Me (3)-03 i-Pr Me (3)-04 n-Bu Me (3)-05
i-Bu Me (3)-06 t-Bu Me (3)-07 n-C.sub.5H.sub.11 Me (3)-08
n-C.sub.6H.sub.13 Me (3)-09 n-C.sub.7H.sub.15 Me (3)-10
n-C.sub.8H.sub.17 Me (3)-11 n-C.sub.9H.sub.19 Me (3)-12
n-C.sub.10H.sub.21 Me (3)-13 n-C.sub.11H.sub.23 Me (3)-14
n-C.sub.12H.sub.25 Me (3)-15 n-C.sub.13H.sub.27 Me (3)-16
n-C.sub.14H.sub.29 CF.sub.3PhSO.sub.2 (3)-17 n-C.sub.16H.sub.33
CF.sub.3PhSO.sub.2 (3)-18 cy-C.sub.5H.sub.9 C.sub.5F.sub.5 (3)-19
cy-C.sub.6H.sub.11 CF.sub.3PhSO.sub.2 (3)-20 cy-C.sub.8H.sub.15
n-C.sub.6F.sub.13 (3)-21 cy-C.sub.10H.sub.19 Me (3)-22 Ph Me (3)-23
4-Tolyl Me (3)-24 PhPh Me (3)-25 1-Nap Me (3)-26 2-Nap Me (3)-27
2-thienyl Me (3)-28 4-HexylPh Me (3)-29 4-OctylPh Me (3)-30
4-DecylPh Me (3)-31 Ph Me (3)-32 4-Tolyl Me (3)-33 PhPh Me (3)-34
1-Nap Me (3)-35 2-Nap Me (3)-36 2-thienyl Me (3)-37 4-HexylPh Me
(3)-38 4-OctylPh Me (3)-39 4-DecylPh Me (3)-40 n-Bu Ph
CF.sub.3SO.sub.2 (3)-41 n-C.sub.6H.sub.13 Ph CF.sub.3SO.sub.2
(3)-42 n-C.sub.8H.sub.17 Ph CF.sub.3SO.sub.2 (3)-43
n-C.sub.10H.sub.21 Ph CF.sub.3SO.sub.2 (3)-44 n-C.sub.12H.sub.25 Ph
CF.sub.3PhSO.sub.2 (3)-45 Ph Ph Me (3)-46 4-Tolyl Ph Me (3)-47 PhPh
Ph Me (3)-48 1-Nap Ph Me (3)-49 2-thienyl Ph Me (3)-50 Ph 4-Tolyl
CF.sub.3SO.sub.2 (3)-51 Ph PhPh CF.sub.3SO.sub.2 (3)-52
n-C.sub.8H.sub.17 n-C.sub.8H.sub.17 CF.sub.3SO.sub.2 (3)-53
n-C.sub.12H.sub.25 n-C.sub.12H.sub.25 CF.sub.3SO.sub.2 (3)-54 Me Me
(3)-55 Me Me (3)-56 Et Me (3)-57 n-Pr Me (3)-58 n-Bu Me (3)-59 i-Bu
Me (3)-60 t-Bu Me (3)-61 n-C.sub.5H.sub.11 Me (3)-62
n-C.sub.6H.sub.13 Me (3)-63 n-C.sub.8H.sub.17 Me (3)-64
n-C.sub.10H.sub.21 Me (3)-65 n-C.sub.12H.sub.25 Me (3)-66
n-C.sub.14H.sub.29 CF.sub.3SO.sub.2 (3)-67 n-C.sub.16H.sub.33
CF.sub.3SO.sub.2 (3)-68 cy-C.sub.5H.sub.9 Me (3)-69
cy-C.sub.6H.sub.11 Me (3)-70 cy-C.sub.8H.sub.15 CF.sub.3SO.sub.2
(3)-71 cy-C.sub.10H.sub.19 CF.sub.3SO.sub.2 (3)-72 Ph
CF.sub.3SO.sub.2 (3)-73 Ph CF.sub.3SO.sub.2 (3)-74 n-Bu
CF.sub.3SO.sub.2 (3)-75 n-C.sub.6H.sub.13 CF.sub.3SO.sub.2 (3)-76
n-C.sub.8H.sub.17 CF.sub.3SO.sub.2 (3)-77 n-C.sub.10H.sub.21
CF.sub.3SO.sub.2 (3)-78 n-C.sub.12H.sub.25 CF.sub.3SO.sub.2 (3)-79
n-C.sub.6H.sub.13 CF.sub.3SO.sub.2 (3)-80 n-C.sub.8H.sub.17
CF.sub.3SO.sub.2 (3)-81 n-C.sub.10H.sub.21 CF.sub.3SO.sub.2 (3)-82
4-Tolyl CF.sub.3SO.sub.2 (3)-83 4-Tolyl CF.sub.3SO.sub.2 (3)-84
PhPh CF.sub.3SO.sub.2 (3)-85 PhPh CF.sub.3SO.sub.2
[0064] Hereinafter, specific examples of the compound (4) as an
intermediate (compounds (4)-01 to (4)-85) will be shown, but the
present invention will not be limited to these. The blank indicates
a hydrogen atom.
##STR00013##
TABLE-US-00003 TABLE 3 Compound No. R.sup.31 R.sup.32 R.sup.4
(4)-01 Et Me (4)-02 n-Pr Me (4)-03 i-Pr Me (4)-04 n-Bu Me (4)-05
i-Bu Me (4)-06 t-Bu Me (4)-07 n-C.sub.5H.sub.11 Me (4)-08
n-C.sub.6H.sub.13 Me (4)-09 n-C.sub.7H.sub.15 Me (4)-10
n-C.sub.8H.sub.17 Me (4)-11 n-C.sub.9H.sub.19 Me (4)-12
n-C.sub.10H.sub.21 Me (4)-13 n-C.sub.11H.sub.23 Me (4)-14
n-C.sub.12H.sub.25 Me (4)-15 n-C.sub.13H.sub.27 Me (4)-16
n-C.sub.14H.sub.29 CF.sub.3PhSO.sub.2 (4)-17 n-C.sub.16H.sub.33
CF.sub.3PhSO.sub.2 (4)-18 cy-C.sub.5H.sub.9 C.sub.6F.sub.5 (4)-19
cy-C.sub.6H.sub.11 CF.sub.3PhSO.sub.2 (4)-20 cy-C.sub.8H.sub.15
n-C.sub.6F.sub.13 (4)-21 cy-C.sub.10H.sub.19 Me (4)-22 Ph Me (4)-23
4-Tolyl Me (4)-24 PhPh Me (4)-25 1-Nap Me (4)-26 2-Nap Me (4)-27
2-thienyl Me (4)-28 4-HexylPh Me (4)-29 4-OctylPh Me (4)-30
4-DecylPh Me (4)-31 Ph Me (4)-32 4-Tolyl Me (4)-33 PhPh Me (4)-34
1-Nap Me (4)-35 2-Nap Me (4)-36 2-thienyl Me (4)-37 4-HexylPh Me
(4)-38 4-OctylPh Me (4)-39 4-DecylPh Me (4)-40 n-Bu Ph
CF.sub.3SO.sub.2 (4)-41 n-C.sub.6H.sub.13 Ph CF.sub.3SO.sub.2
(4)-42 n-C.sub.8H.sub.17 Ph CF.sub.3SO.sub.2 (4)-43
n-C.sub.10H.sub.21 Ph CF.sub.3SO.sub.2 (4)-44 n-C.sub.12H.sub.25 Ph
CF.sub.3PhSO.sub.2 (4)-45 Ph Ph Me (4)-46 4-Tolyl Ph Me (4)-47 PhPh
Ph Me (4)-48 1-Nap Ph Me (4)-49 2-thienyl Ph Me (4)-50 Ph 4-Tolyl
CF.sub.3SO.sub.2 (4)-51 Ph PhPh CF.sub.3SO.sub.2 (4)-52
n-C.sub.8H.sub.17 n-C.sub.8H.sub.17 CF.sub.3SO.sub.2 (4)-53
n-C.sub.12H.sub.25 n-C.sub.12H.sub.25 CF.sub.3SO.sub.2 (4)-54 Me Me
(4)-55 Me Me (4)-56 Et Me (4)-57 n-Pr Me (4)-58 n-Bu Me (4)-59 i-Bu
Me (4)-60 t-Bu Me (4)-61 n-C.sub.5H.sub.11 Me (4)-62
n-C.sub.6H.sub.13 Me (4)-63 n-C.sub.8H.sub.17 Me (4)-64
n-C.sub.10H.sub.21 Me (4)-65 n-C.sub.12H.sub.25 Me (4)-66
n-C.sub.14H.sub.29 CF.sub.3SO.sub.2 (4)-67 n-C.sub.16H.sub.33
CF.sub.3SO.sub.2 (4)-68 cy-C.sub.5H.sub.9 Me (4)-69
cy-C.sub.6H.sub.11 Me (4)-70 cy-C.sub.8H.sub.15 CF.sub.3SO.sub.2
(4)-71 cy-C.sub.10H.sub.19 CF.sub.3SO.sub.2 (4)-72 Ph
CF.sub.3SO.sub.2 (4)-73 Ph CF.sub.3SO.sub.2 (4)-74 n-Bu
CF.sub.3SO.sub.2 (4)-75 n-C.sub.6H.sub.13 CF.sub.3SO.sub.2 (4)-76
n-C.sub.8H.sub.17 CF.sub.3SO.sub.2 (4)-77 n-C.sub.10H.sub.21
CF.sub.3SO.sub.2 (4)-78 n-C.sub.12H.sub.25 CF.sub.3SO.sub.2 (4)-79
n-C.sub.6H.sub.13 CF.sub.3SO.sub.2 (4)-80 n-C.sub.8H.sub.17
CF.sub.3SO.sub.2 (4)-81 n-C.sub.10H.sub.21 CF.sub.3SO.sub.2 (4)-82
4-Tolyl CF.sub.3SO.sub.2 (4)-83 4-Tolyl CF.sub.3SO.sub.2 (4)-84
PhPh CF.sub.3SO.sub.2 (4)-85 PhPh CF.sub.3SO.sub.2
[0065] Next, the reaction formula (4) will be specifically
described. The reaction is a novel reaction. In the compound (3) as
the starting material in which an oxygen atom is bonded at the
2-position, the 3-position is highly selectively SMethylated using
dimethyl disulfide (Me.sub.2S.sub.2). To develop this reaction, the
present inventors studied the base for metalating by hydrogen
drawing (alkyl metal reagent, alkyl earth metal reagent) at the
3-position, the reaction solvent, the reaction temperature, and the
operation procedure, and found out a production method for highly
selectively SMethylating the compound (3) at 3-position using
dimethyl disulfide.
##STR00014##
[0066] The base used for the reaction is desirably an alkali metal
reagent, that is, a lithium reagent, a sodium reagent, and a
potassium reagent; and an alkyl earth metal reagent, that is, a
magnesium reagent and a calcium reagent. Specifically,
methyllithium, n-butyllithium, t-butyllithium, phenyllithium,
methylmagnesium chloride, butylmagnesium chloride, and the like can
be used. Particularly preferably, use of butyllithium is desirable
because it is a stable and strong base.
[0067] The amount of the base to be used is desirably 0.5 mol or
more and 10 mol or less based on 1 mol of the compound (3). The
base may be further added in the range of the above amount to the
reaction solution prepared by adding the compound (3) to the base.
By adding the base in two steps as above, the hydrogen atom at the
3-position in the compound (3) may be smoothly drawn.
[0068] In the method for producing the compound according to the
present embodiment, a basic compound (an additive) may be added
together with the alkyl metal reagent for stabilization of the
lithium reagent and the like. Examples of the basic compound can
include N,N,N'-trimethylethylenediamine, dimethylamine,
diisopropylamine, and morpholine.
[0069] The reaction is desirably carried out under an inert gas
atmosphere such as under an argon atmosphere, under a nitrogen
replacement, under a dry argon atmosphere, and under a dry nitrogen
stream.
[0070] The reaction temperature in reacting the compound (3) with
the base is preferably in the range of -100.degree. C. to
30.degree. C., and more preferably -80.degree. C. to 10.degree.
C.
[0071] In the reaction, any solvent can be used. Desirably, the
solvent to be used is an ether solvent, an aliphatic solvent, or an
aromatic solvent. These solvents are desirably dehydrated and
used.
[0072] Examples of the ether solvent to be used for the reaction
include tetrahydrofuran (THF), diethyl ether, dimethoxyethane, and
dioxane. Examples of the aliphatic solvent include n-pentane,
n-hexane, and n-heptane. Examples of the aromatic solvent include
toluene and xylene.
[0073] The amount of dimethyl disulfide to be used in the reaction
is desirably 0.5 mol or more and 10 mol or less based on 1 mol of
the compound (3).
[0074] In refining the compound (4) obtained above, the refining
method is not particularly limited. A known refining method can be
used depending on the physical properties of the compound.
Specifically, the compound can be refined by recrystallization,
column chromatography, and the like.
[0075] The reaction for highly selective SMethylation at the
3-position of the compound (3) having an oxygen atom at the
2-position by using dimethyl disulfide had not been known in the
related art. To develop the reaction, the present inventors studied
the base for metalating to the 3-position by hydrogen drawing as
above (alkyl metal reagent, alkyl earth metal reagent), the
reaction solvent, the reaction temperature, and the operation
procedure, and as a result, found out the method for highly
selective SMethylation at the 3-position in the compound (3) using
dimethyl disulfide, namely, the method for highly selectively
producing the compound (4).
[0076] Subsequently, the compound (5) to be reacted with the
compound (4) and the compound (6) as a product of the reaction
formula (5) will be described.
[0077] In the formula (5) that is a tin compound, R.sup.5
represents an alkyl group. Examples of the alkyl group include
linear or branched alkyl groups. The alkyl groups have 1 to 8
carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 4
carbon atoms. Here, specific examples of the linear alkyl group
include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl.
Specific examples of the branched alkyl group include C3-C6
saturated branched alkyl groups such as i-propyl, i-butyl, t-butyl,
i-pentyl, and i-hexyl. An n-butyl group is preferable because of
its availability.
[0078] Hereinafter, specific examples of the tin compound
represented by the formula (5) will be shown, but the present
invention will not be limited to these.
##STR00015##
TABLE-US-00004 TABLE 4 Compound No. R.sup.5 (5)-01 Me (5)-02 Et
(5)-03 n-Pr (5)-04 i-Pr (5)-05 n-Bu (5)-06 i-Bu (5)-07 t-Bu
[0079] R.sup.3 (R.sup.31 and R.sup.32) in the compound (6) means
the same as R.sup.3 (R.sup.31 and R.sup.32) in the compound
(3).
[0080] Hereinafter, specific examples of the compound (6)
(compounds (6)-01 to (6)-71) will be shown, but the present
invention will not be limited to these. R.sup.3 in the compound (6)
is also written as R.sup.31 and R.sup.32 for convenience.
##STR00016##
TABLE-US-00005 TABLE 5 Compound No. R.sup.31 R.sup.32 (6)-01 Et
(6)-02 n-Pr (6)-03 i-Pr (6)-04 n-Bu (6)-05 i-Bu (6)-06 t-Bu (6)-07
n-C.sub.5H.sub.11 (6)-08 n-C.sub.6H.sub.13 (6)-09 n-C.sub.7H.sub.15
(6)-10 n-C.sub.8H.sub.17 (6)-11 n-C.sub.9H.sub.19 (6)-12
n-C.sub.10H.sub.21 (6)-13 n-C.sub.11H.sub.23 (6)-14
n-C.sub.12H.sub.25 (6)-15 n-C.sub.13H.sub.27 (6)-16
n-C.sub.14H.sub.29 (6)-17 n-C.sub.16H.sub.33 (6)-18
cy-C.sub.5H.sub.9 (6)-19 cy-C.sub.6H.sub.11 (6)-20
cy-C.sub.8H.sub.15 (6)-21 cy-C.sub.10H.sub.19 (6)-22 Ph (6)-23
4-Tolyl (6)-24 PhPh (6)-25 1-Nap (6)-26 2-Nap (6)-27 2-thienyl
(6)-28 4-HexylPh (6)-29 4-OctylPh (6)-30 4-DecylPh (6)-31 Ph (6)-32
4-Tolyl (6)-33 PhPh (6)-34 1-Nap (6)-35 2-Nap (6)-36 2-thienyl
(6)-37 4-HexylPh (6)-38 4-OctylPh (6)-39 4-DecylPh (6)-40 n-Bu Ph
(6)-41 n-C.sub.6H.sub.13 Ph (6)-42 n-C.sub.8H.sub.17 Ph (6)-43
n-C.sub.10H.sub.21 Ph (6)-44 n-C.sub.12H.sub.25 Ph (6)-45 Ph Ph
(6)-46 4-Tolyl Ph (6)-47 PhPh Ph (6)-48 1-Nap Ph (6)-49 2-thienyl
Ph (6)-50 Ph 4-Tolyl (6)-51 Ph PhPh (6)-52 n-C.sub.8H.sub.17
n-C.sub.8H.sub.17 (6)-53 n-C.sub.12H.sub.25 n-C.sub.12H.sub.25
(6)-54 Me (6)-55 Me (6)-56 Et (6)-57 n-Pr (6)-58 n-Bu (6)-59 i-Bu
(6)-60 t-Bu (6)-61 n-C.sub.5H.sub.11 (6)-62 n-C.sub.6H.sub.13
(6)-63 n-C.sub.8H.sub.17 (6)-64 n-C.sub.10H.sub.21 (6)-65
n-C.sub.12H.sub.25 (6)-66 n-C.sub.14H.sub.29 (6)-67
n-C.sub.16H.sub.33 (6)-68 cy-C.sub.5H.sub.9 (6)-69
cy-C.sub.6H.sub.11 (6)-70 cy-C.sub.8H.sub.15 (6)-71
cy-C.sub.10H.sub.19
[0081] In the conventional techniques, a raw material aldehyde body
for synthesizing the compound (6) (the compound (B) in the reaction
formula 2) is very difficult to synthesize (Patent Literature 3 and
Non Patent Literature 1). In the present invention, the compound
(5) is reacted when the oxygen atoms at the 2-positions in the two
molecules of compound (4) having an MeS group at the 3-position are
eliminated. This reaction enables highly selective production of
the compound (6) (see the reaction formula (5)). Usually, the
reaction shown in the reaction formula (5) uses a Pd compound as a
catalyst. Pd is easily poisoned by a sulfur compound, and may lose
activity quickly. For this reason, the present inventors studied
the catalyst, reaction solvent, reaction temperature, and operation
procedure that allowed oxygen in the compound (4) to be effectively
eliminated and the compound (4) to react with the compound (5) as
above, and found out the production method that can produce the
compound (6) from the two molecules of compound (4) at a high
selectively and at a high yield.
[0082] Hereinafter, the reaction formula (5) will be specifically
described.
##STR00017##
[0083] Here, R.sup.4 in the compound (4) can be converted to an
optimal substituent when necessary for use when the reaction shown
in the reaction formula (5) is carried out. Namely, R.sup.4 can be
converted properly as shown in Examples.
[0084] In the reaction shown in the reaction formula (5), the
mixing ratio of the compound (4) to the compound (5) is preferably
1.8 mol to 2.5 mol based on 1 mol of the compound (5). The reaction
is carried out at the mixing ratio of more preferably 1.95 mol to
2.10 mol, and still more preferably 1.95 mol to 2.05 mol.
[0085] Alternatively, first, the compound (4) can be reacted with
the compound (5) at a proportion of approximately 1:1.
Subsequently, the compound (4) having a different substituent from
that in the compound (4) previously added is added, and the
reaction is carried out. This can synthesize an asymmetric
intermediate (6).
[0086] The catalyst used in the reaction can be any Pd or Ni
catalyst. At least one catalyst may contain at least one compound
selected from the group consisting of nickel and palladium
catalysts having a ligand selected from the group consisting of
tri-tert-butylphosphine, triadamantylphosphine,
1,3-bis(2,4,6-trimethylphenyl)imidazolidinium chloride,
1,3-bis(2,6-diisopropylphenyl)imidazolidinium chloride,
1,3-diadamantylimidazolidinium chloride, or a mixture thereof;
metal Pd, Pd/C (hydrous or nonhydrous), bis(triphenyl
phosphino)palladium dichloride (Pd(PPh.sub.3).sub.2Cl.sub.2),
palladium(II) acetate (Pd(OAc).sub.2),
tetrakis(triphenylphosphine)palladium (Pd(PPh.sub.3).sub.4),
tetrakis(triphenylphosphine)nickel (Ni(PPh.sub.3).sub.4),
nickel(II) acetylacetonate Ni(acac).sub.2,
dichloro(2,2'-bipyridine)nickel,
dibromobis(triphenylphosphine)nickel (Ni(PPh.sub.3).sub.2Br.sub.2),
bis(diphenylphosphino)propanenickel dichloride (Ni((dppp)Cl.sub.2),
bis(diphenylphosphino)ethanenickel dichloride Ni(dppe)Cl.sub.2, and
a mixture thereof. Examples of preferable catalysts include Pd/C
(hydrous or nonhydrous), Pd(PPh.sub.3).sub.2Cl.sub.2, and
Pd(PPh.sub.3).sub.4, and examples of more preferable catalysts
include Pd(PPh.sub.3).sub.2Cl.sub.2 and Pd(PPh.sub.3).sub.4.
[0087] The amount of the catalyst to be used is desirably 0.001 mol
or more and 0.5 mol or less based on 1 mol of the compound (4). The
catalyst may be added in the range of the amount used above to the
reaction solution prepared by adding the compound (4), the compound
(5), and the catalyst. When the catalyst is poisoned by sulfur or
the like to deactivate the catalyst, addition of the catalyst in
two or more steps is effective because such operation may prevent
reduction in the reaction rate.
[0088] The reaction temperature in reacting the compound (4) with
the compound (5) is usually -10.degree. C. to 200.degree. C. The
reaction temperature is more preferably 40.degree. C. to
180.degree. C., and still more preferably 80.degree. C. to
150.degree. C.
[0089] The reaction is desirably carried out under an inert gas
atmosphere such as under an argon atmosphere, under nitrogen
replacement, under a dry argon atmosphere, and under a dry nitrogen
stream.
[0090] In the reaction, the solvent may or may not be used. Any
solvent can be used as long as it is a solvent used in typical
organic synthesis. Examples of the solvent can include aromatic
compounds such as chlorobenzene, o-dichlorobenzene, bromobenzene,
nitrobenzene, toluene, and xylene; saturated aliphatic hydrocarbons
such as n-hexane, n-heptane, and n-pentane; alicyclic hydrocarbons
such as cyclohexane, cycloheptane, and cyclopentane; saturated
aliphatic halogenated hydrocarbons such as n-propyl bromide,
n-butyl chloride, n-butyl bromide, dichloromethane, dibromomethane,
dichloropropane, dibromopropane, dichloroethane, dibromoethane,
dichloropropane, dibromopropane, dichlorobutane, chloroform,
bromoform, carbon tetrachloride, carbon tetrabromide,
trichloroethane, tetrachloroethane, and pentachloroethane;
halogenated cyclic hydrocarbons such as chlorocyclohexane,
chlorocyclopentane, and bromocyclopentane; esters such as ethyl
acetate, propyl acetate, butyl acetate, methyl propionate, ethyl
propionate, propyl propionate, butyl propionate, methyl butyrate,
ethyl butyrate, propyl butyrate, and butyl butyrate; and ketones
such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
These solvents may be used singly, or may be used by mixing two or
more.
[0091] At least one high boiling point solvent having a boiling
point of 100.degree. C. or more is preferably used as the reaction
solvent because the reaction rate significantly improves or the
selectivity of the reaction increases.
[0092] The high boiling point solvent having a boiling point of
100.degree. C. or more is preferably amides (N-methyl-2-pyrrolidone
(hereinafter, NMP), N,N-dimethylformamide (hereinafter, abbreviated
to DMF), N,N-dimethylacetamide (hereinafter, DMAc)); glycols
(ethylene glycol, propylene glycol, and polyethylene glycol); and
sulfoxides (dimethyl sulfoxide (hereinafter, abbreviated to DMSO)),
and more preferably N-methyl-2-pyrrolidone, N,N-dimethylformamide,
and N,N-dimethylacetamide.
[0093] In refining of the obtained compound (6), the refining
method is not particularly limited. A known refining method can be
used depending on the properties of the compound (6). Specifically,
the compound can be refined by recrystallization, column
chromatography, and the like.
[0094] Next, the reaction formula (6) will be described.
Hereinafter, specific examples of the compound (2) obtained by
cyclizing the compound (6) obtained by the reaction shown in the
reaction formula (5) will be described, but the present invention
will not be limited to these. The compounds (2)-01 to 53 are the
same compounds as the compounds (1)-01 to 53. Hereinafter, the
compounds are referred using the compounds (1)-01 to 53. The
production method of the present invention can provide the compound
(2) at a high yield from the compound (6) by the same method
specifically described in Non Patent Literature 1, Patent
Literature 3, Patent Literature 6, Patent Literature 7, and Patent
Literature 8. In the compound (2), R.sup.3 is written as R.sup.31
and R.sup.32 for convenience.
##STR00018##
TABLE-US-00006 TABLE 6 Compound No. R.sup.31 R.sup.32 (2)-01 Et
(2)-02 n-Pr (2)-03 i-Pr (2)-04 n-Bu (2)-05 i-Bu (2)-06 t-Bu (2)-07
n-C.sub.5H.sub.11 (2)-08 n-C.sub.6H.sub.13 (2)-09 n-C.sub.7H.sub.15
(2)-10 n-C.sub.8H.sub.17 (2)-11 n-C.sub.9H.sub.19 (2)-12
n-C.sub.10H.sub.21 (2)-13 n-C.sub.11H.sub.23 (2)-14
n-C.sub.12H.sub.25 (2)-15 n-C.sub.13H.sub.27 (2)-16
n-C.sub.14H.sub.29 (2)-17 n-C.sub.16H.sub.33 (2)-18
cy-C.sub.5H.sub.9 (2)-19 cy-C.sub.6H.sub.11 (2)-20
cy-C.sub.8H.sub.15 (2)-21 cy-C.sub.10H.sub.19 (2)-22 Ph (2)-23
4-Tolyl (2)-24 PhPh (2)-25 1-Nap (2)-26 2-Nap (2)-27 2-thienyl
(2)-28 4-HexylPh (2)-29 4-OctylPh (2)-30 4-DecylPh (2)-31 Ph (2)-32
4-Tolyl (2)-33 PhPh (2)-34 1-Nap (2)-35 2-Nap (2)-36 2-thienyl
(2)-37 4-HexylPh (2)-38 4-OctylPh (2)-39 4-DecylPh (2)-40 n-Bu Ph
(2)-41 n-C.sub.6H.sub.13 Ph (2)-42 n-C.sub.8H.sub.17 Ph (2)-43
n-C.sub.10H.sub.21 Ph (2)-44 n-C.sub.12H.sub.25 Ph (2)-45 Ph Ph
(2)-46 4-Tolyl Ph (2)-47 PhPh Ph (2)-48 1-Nap Ph (2)-49 2-thienyl
Ph (2)-50 Ph 4-Tolyl (2)-51 Ph PhPh (2)-52 n-C.sub.8H.sub.17
n-C.sub.8H.sub.17 (2)-53 n-C.sub.12H.sub.25 n-C.sub.12H.sub.25
(2)-54 Me (2)-55 Me (2)-56 Et (2)-57 n-Pr (2)-58 n-Bu (2)-59 i-Bu
(2)-60 t-Bu (2)-61 n-C.sub.5H.sub.11 (2)-62 n-C.sub.6H.sub.13
(2)-63 n-C.sub.8H.sub.17 (2)-64 n-C.sub.10H.sub.21 (2)-65
n-C.sub.12H.sub.25 (2)-66 n-C.sub.14H.sub.29 (2)-67
n-C.sub.16H.sub.33 (2)-68 cy-C.sub.5H.sub.9 (2)-69
cy-C.sub.6H.sub.11 (2)-70 cy-C.sub.8H.sub.15 (2)-71
cy-C.sub.10H.sub.19
[0095] The field effect transistor of the present invention (Field
effect transistor, hereinafter, abbreviated to FET in some cases)
has two electrodes (source electrode and drain electrode)
contacting the semiconductor. The current flowing between the
electrodes is controlled by the voltage applied to another
electrode called the gate electrode.
[0096] Typically, the structure of the field effect transistor
often used is the structure (Metal-Insulator-Semiconductor; MIS
structure) in which the gate electrode is insulated with an
insulation film. The structure of the field effect transistor using
a metal oxide film as the insulation film is called a MOS
structure. Besides, another known structure is the structure in
which the gate electrode is formed with a Schottky barrier being
interposed, namely, a MES structure. The MIS structure is often
used for the FET using an organic semiconductor material.
[0097] Hereinafter, using the drawings, the organic field effect
transistor according to the present invention will be more
specifically described, but the present invention will not be
limited to these structures.
[0098] Some examples of embodiments of the field effect transistor
according to the present invention (element) are shown in FIG. 1.
In the respective examples, a source electrode 1, a semiconductor
layer 2, a drain electrode 3, an insulator layer 4, a gate
electrode 5, and a substrate 6 are shown. The arrangement of the
respective layers and electrodes can be properly selected depending
on the application of the element. These field effect transistors
shown in schematic views A to D are called the lateral FET in which
the current flows in the direction parallel to the substrate. The
structure shown in the schematic view A is called the bottom
contact structure, and the structure shown in the schematic view B
is called the top contact structure. The structure shown in the
schematic view C is a structure often used in creation of an
organic single-crystal FET, in which source and drain electrodes,
and an insulator layer are provided on a semiconductor and a gate
electrode is formed thereon. The structure shown in the schematic
view D is a structure called the top & bottom contact type
transistor. The schematic view E is a schematic view showing an FET
having a vertical structure, namely, a static induction transistor
(SIT). In the SIT, the flow of the current extends planarly, a
large amount of carriers can move at one time. The source electrode
and the drain electrode are arranged vertically. This arrangement
can reduce the distance between the electrodes, attaining fast
response. Consequently, the SIT is preferably used in applications
in which a large amount of current is flown, high-speed switching
is performed, or the like. In E of FIG. 1, no substrate is shown.
In typical cases, substrates are provided on the outer sides of the
source and drain electrodes 1 and 3 in E of FIG. 1.
[0099] Components in the examples of the respective embodiments
will be described.
[0100] The substrate 6 needs to hold the layers to be formed
thereon without the layers being peeled off. For the substrate 6,
insulation materials such as resin plates and films, paper, glass,
quartz, and ceramics; a conductive substrate made of a metal, an
alloy, or the like and having an insulator layer formed thereon by
coating or the like; materials formed of a combination of various
materials such as a resin and an inorganic material; and the like
can be used, for example. Examples of usable resin films include
polyethylene terephthalate, polyethylene naphthalate,
polyethersulfone, polyamide, polyimide, polycarbonate, cellulose
triacetate, and polyetherimide. Use of the resin film or paper can
provide flexibility of the element, and can attain a flexible and
light element. Practicality also improves. The thickness of the
substrate is usually 1 .mu.m to 10 mm, and preferably 5 .mu.m to 5
mm
[0101] A conductive material is used for the source electrode 1,
the drain electrode 3, and the gate electrode 5. For example,
metals such as platinum, gold, silver, aluminum, chromium,
tungsten, tantalum, nickel, cobalt, copper, iron, lead, tin,
titanium, indium, palladium, molybdenum, magnesium, calcium,
barium, lithium, potassium, sodium and alloys containing these;
conductive oxides such as InO.sub.2, ZnO.sub.2, SnO.sub.2, and ITO;
conductive high-molecular compounds such as polyaniline,
polypyrrole, polythiophene, polyacetylene, poly-paraphenylene,
vinylene, and polydiacetylene; semiconductors such as silicon,
germanium, and gallium arsenic; carbon materials such as carbon
black, fullerene, carbon nanotube, and graphite; and the like can
be used. The conductive high-molecular compound or the
semiconductor may be doped. Examples of the dopant include
inorganic acids such as hydrochloric acid and sulfuric acid;
organic acids having an acidic functional group such as sulfonic
acid; Lewis acids such as PF.sub.5, AsF.sub.5, and FeCl.sub.3;
halogen atoms such as iodine; and metal atoms such as lithium,
sodium, and potassium. Boron, phosphorus, arsenic, and the like are
often used as a dopant for an inorganic semiconductor such as
silicon. A conductive composite material prepared by dispersing
carbon black or a metal particle in the dopant also is used.
[0102] The source and drain electrodes contact the semiconductor
substance directly and have a role to inject charges such as
electrons or holes into the semiconductor. To reduce the contact
resistance to facilitate injection of charges, it is important to
match the HOMO level and LUMO level of the semiconductor material
with the work function of the electrode. To reduce the contact
resistance to provide an ohmic element, semiconductor properties
can be improved by interposing of an injection improvement layer
formed of a material such as molybdenum oxide and tungsten oxide,
doping of the metal electrode, surface modification by a
single-molecular film, or the like.
[0103] The distance between the source electrode and the drain
electrode (channel length) is an important factor that determines
the properties of the element. The channel length is usually 0.1 to
300 .mu.m, and preferably 0.5 to 100 .mu.m. As the channel length
is shorter, the amount of the current to be extracted increases but
leakage current or the like occurs. For this reason, a proper
channel length needs to be set. The width between the source
electrode and the drain electrode (channel width) is usually 10 to
5000 .mu.m, and preferably 100 to 2000 .mu.m. The channel width can
be longer by using a combed structure for the structure of the
electrode or the like. The channel width may be properly set
depending on the amount of the current needed, the structure of the
element, and the like.
[0104] The structures (shapes) of the source electrode and drain
electrode will be described. The structure of the source electrode
and that of the drain electrode may be the same or different from
each other. For the bottom contact structure, usually, the
respective electrodes are preferably created using lithography, and
formed into a rectangular parallelepiped. The length of the
electrode may be equal to the channel width. The width of the
electrode is not particularly limited. Preferably, the width is
shorter for the purpose of reducing the area of the element in the
range in which electrical properties can be stabilized. The width
of the electrode is usually 0.1 to 1000 .mu.m, and preferably 0.5
to 100 .mu.m. The thickness of the electrode is usually 0.1 to 1000
nm, preferably 1 to 500 nm, and more preferably 5 to 200 nm. The
electrodes 1, 3, and 5 each have wiring connected thereto. The
wiring also is created using substantially the same material as
that for the electrode.
[0105] For the insulator layer 4, a material having insulation
properties is used. For example, polymers such as
poly(para-xylylene), polyacrylate, polymethyl methacrylate,
polystyrene, polyvinyl phenol, polyamide, polyimide, polycarbonate,
polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane,
polysulfone, epoxy resins, phenol resins, fluorine resins and
copolymers in combination thereof; metal oxides such as silicon
dioxide, aluminum oxide, titanium oxide, and tantalum oxide;
ferroelectric metal oxides such as SrTiO.sub.3 and BaTiO.sub.3;
nitrides such as silicon nitride and aluminum nitride; sulfides;
dielectric substances such as fluoride; or polymers prepared by
dispersing particles of these dielectric substances; and the like
can be used. The film thickness of the insulator layer 4 depends on
the material, and is usually 0.1 nm to 100 .mu.m, preferably 0.5 nm
to 50 .mu.m, and more preferably 1 nm to 10 .mu.m.
[0106] For the semiconductor layer 2 in the present invention, an
organic thin film comprising one or two or more heterocyclic
compounds represented by the compound (1) above is used. The
compound in the organic thin film may be a mixture. Preferably, the
organic thin film contains usually 50% by mass or more, preferably
80% by mass or more, and still more preferably 95% by mass or more
of the compound (1).
[0107] The field effect transistor of the present invention uses an
organic thin film formed of at least one heterocyclic compound
represented by the compound (1) as the semiconductor material.
Substantially, the semiconductor material made of a single
heterocyclic compound is preferably used rather than the
semiconductor material made of a mixture of a plurality of
heterocyclic compounds represented by the compound (1).
[0108] To improve the properties of the field effect transistor or
give other properties, however, other organic semiconductor
materials and a variety of additives may be mixed when
necessary.
[0109] The additives can be added in the range of usually 0.01 to
10% by mass, preferably 0.05 to 5% by mass, and more preferably 0.1
to 3% by mass based on the total amount of the semiconductor
material.
[0110] The semiconductor layer may be composed of a plurality of
organic thin film layers, but the semiconductor layer more
preferably has a single layer structure.
[0111] The film thickness of the semiconductor layer 2 is
preferably thinner in the range in which the necessary function is
not lost. The reason is as follows: in the lateral field effect
transistors shown in the schematic views A, B, and D, when the
semiconductor layer has a predetermined film thickness or more, the
properties of the element do not depend on the film thickness;
meanwhile, a thicker film thickness often increases leakage
current. The film thickness of the semiconductor layer for
exhibiting the necessary function is usually 1 nm to 10 .mu.m,
preferably 5 nm to 5 .mu.m, and more preferably 10 nm to 3
.mu.m.
[0112] The field effect transistor of the present invention can
have other layers provided between the substrate and the insulation
film layer, between the insulation film layer and the semiconductor
layer, or on the outer surface of the element, for example, when
necessary. For example, a protective layer is formed on the
semiconductor layer directly or with another layer being
interposed. The protective layer can reduce the influence of
outside air such as humidity, and increase the ON/OFF ratio of the
element. Thus, the protective layer can advantageously stabilize
electrical properties.
[0113] The material for the protective layer is not particularly
limited. For example, films formed of a variety of resins such as
an acrylic resin such as an epoxy resin and polymethyl
methacrylate, polyurethane, polyimide, polyvinyl alcohol, a
fluorinated resin, and polyolefin; inorganic oxide films formed of
silicon oxide, aluminum oxide, silicon nitride, or the like; and
films formed of a dielectric substance such as nitride films; and
the like are preferably used. Particularly, resins (polymers)
having a low permeability or absorption rate of oxygen or moisture
are preferable. A protective material developed for organic EL
displays has also recently been able to be used. Any film thickness
of the protective layer can be selected according to the purpose.
The film thickness is usually 100 nm to 1 mm
[0114] The substrate or insulator layer on which the semiconductor
layer is laminated can be subjected to a surface treatment in
advance to improve film forming properties of the semiconductor
material and the properties of the element. Particularly, the
properties of the organic semiconductor material may change
depending on the state of the film such as orientation of the
molecule. For example, by adjusting the degree of
hydrophilicity/hydrophobicity of the substrate surface, the
properties of the film to be formed on the substrate can be
improved. Particularly, the properties of the organic semiconductor
material may significantly change depending on the state of the
film such as orientation of the molecule. Probably, for this
reason, the surface treatment of the substrate can improve in the
properties such as carrier mobility because the surface treatment
controls orientation of the molecule at the interface between the
substrate or the like and the semiconductor layer to be formed
thereon, or reduces trap sites on the substrate or insulator
layer.
[0115] The trap site means a functional group existing in the
non-treated substrate such as a hydroxyl group. If such a
functional group exists, the functional group attracts electrons,
reducing carrier mobility. Consequently, reduction in the trap site
is also effective in improving properties such as carrier mobility
in many cases.
[0116] Examples of the treatment of the substrate for improving the
properties include a hydrophobization treatment using
hexamethyldisilazane, cyclohexene, octyltrichlorosilane,
octadecyltrichlorosilane, or the like; an acid treatment using
hydrochloric acid, sulfuric acid, acetic acid, and the like; an
alkali treatment using sodium hydroxide, potassium hydroxide,
calcium hydroxide, ammonia, or the like; an ozone treatment; a
fluorination treatment; a plasma treatment using oxygen, argon, or
the like; a Langmuir-Blodgett film forming treatment; a treatment
of forming a thin film of other insulators or semiconductors;
mechanical treatment; an electrical treatment such as corona
discharge; or a rubbing treatment using fibers or the like.
However, the field effect transistor using the compound of the
present invention has a small influence of the material over the
substrate or insulator layer. This feature eliminates more
expensive treatments and adjustment of the state of the surface,
and enables use of a broader range of materials, leading to general
versatility and cost reduction.
[0117] In these embodiments, as a method for forming the layers
such as an insulation film layer and a semiconductor layer, a
vacuum evaporation method, a sputter method, a coating method, a
printing method, a sol-gel method, and the like can be properly
used, for example.
[0118] Next, the method for producing a field effect transistor
according to the present invention will be described below based on
FIG. 2 using the bottom contact type field effect transistor (FET)
shown in Embodiment A in FIG. 1 as an example.
[0119] The production method can be used for the field effect
transistor according to other embodiments.
(Substrate and Treatment of Substrate)
[0120] The field effect transistor of the present invention is
created by forming a variety of necessary layers and electrodes on
the substrate 6 (see (1) of FIG. 2). The substrate described above
can be used. The substrate can be subjected to the surface
treatment described above. The thickness of the substrate 6 is
preferably thinner in the range in which the necessary function is
not inhibited. Depending on the material, the thickness is usually
1 .mu.m to 10 mm, and preferably 5 .mu.m to 5 mm. The substrate may
function as an electrode when necessary.
(Formation of Gate Electrode)
[0121] The gate electrode 5 is formed on the substrate 6 (see (2)
of FIG. 2). The electrode material described above is used. For the
method for forming an electrode film, a variety of methods can be
used: for example, a vacuum evaporation method, a sputter method, a
coating method, a thermal transfer method, a printing method, a
sol-gel method, and the like. During or after film formation,
patterning is preferably performed when necessary to have a desired
shape. Moreover, a variety of patterning methods can be used.
Examples thereof include photolithography using patterning and
etching of a photoresist in combination. The patterning can also be
performed using a printing method such as inkjet printing, screen
printing, offset printing, and relief printing, a soft lithography
method such as a microcontact printing method, and a method using
these in combination. The film thickness of the gate electrode 5
depends on the material, and is usually 0.1 nm to 10 .mu.m,
preferably 0.5 nm to 5 .mu.m, and more preferably 1 nm to 1 .mu.m.
The film thickness may be larger than above when the substrate
functions as the gate electrode.
(Formation of Insulator Layer)
[0122] The insulator layer 4 is formed on the gate electrode 5 (see
(3) of FIG. 2). The insulator material described above is used, for
example. In formation of the insulator layer 4, a variety of
methods can be used. Examples of the method include coating methods
such as spin coating, spray coating, dip coating, casting, bar
coating, and blade coating; printing methods such as screen
printing, offset printing, and inkjet printing; and dry process
methods such as a vacuum evaporation method, a molecular beam
epitaxial growth method, an ion cluster beam method, an ion plating
method, a sputtering method, an atmospheric pressure plasma method,
and a CVD method. Besides, a sol-gel method, a method for forming
an oxide film on a metal, for example, forming anodized aluminum on
aluminum or silicon dioxide on silicon, and the like are used.
[0123] In the portion in which the insulator layer contacts the
semiconductor layer, the insulator layer may be subjected to a
predetermined surface treatment to well orient the molecule that
constitutes the semiconductor at the interface between these layers
such as the molecule of the heterocyclic compound represented by
the compound (1). For the method for the surface treatment, the
same method as the surface treatment of the substrate can be used.
The film thickness of the insulator layer 4 is preferably thinner
in the range in which the function is not impaired. The film
thickness is usually 0.1 nm to 100 .mu.m, preferably 0.5 nm to 50
.mu.m, and more preferably 5 nm to 10 .mu.m.
(Formation of Source Electrode and Drain Electrode)
[0124] The source electrode 1 and the drain electrode 3 can be
formed according to the method for producing the gate electrode 5
(see (4) of FIG. 2).
(Formation of Semiconductor Layer)
[0125] An organic thin film comprising one or two or more
heterocyclic compounds represented by the compound (1) is formed on
the insulator layer 4, the source electrode 1, and the drain
electrode 3 as a semiconductor layer. For the semiconductor
material, an organic material containing usually the total amount
of 50% by mass or more of one heterocyclic compound represented by
the compound (1) or a mixture of the heterocyclic compounds is used
as described above. In formation of the semiconductor layer, a
variety of methods can be used. The methods are mainly classified
into vacuum process formation methods such as a sputtering method,
a CVD method, a molecular beam epitaxial growth method, and a
vacuum evaporation method; coating methods such as a dip coating
method, a die coater method, a roll coater method, a bar coater
method, and a spin coating method; solution process formation
methods such as an inkjet method, a screen printing method, an
offset printing method, and a microcontact printing method.
[0126] When the organic thin film functioning as the semiconductor
layer is formed using the heterocyclic compound represented by the
compound (1) of the present invention as the semiconductor
material, a method for forming the organic thin film formed by the
vacuum process as the semiconductor layer is preferable, and the
vacuum evaporation method is more preferable. Film formation by the
solution process can be used, and an inexpensive printing method
can be used.
[0127] A method for forming a film using an organic material by a
vacuum process to obtain an organic thin film will be
described.
[0128] In the present invention, the method for heating the organic
material in a crucible or a metal boat under vacuum, and applying
(depositing) the evaporated organic material onto a substrate
(exposed portions of the insulator layer, the source electrode, and
the drain electrode), namely, the vacuum evaporation method is
preferably used. At this time, the degree of vacuum is usually
1.0.times.10.sup.-1 Pa or less, and preferably 1.0.times.10.sup.-3
Pa or less. The substrate temperature during deposition may change
the organic semiconductor film, and the properties of the field
effect transistor as a result. The substrate temperature needs to
be carefully selected. The substrate temperature during deposition
is usually 0 to 200.degree. C., preferably 10 to 150.degree. C.,
more preferably 15 to 120.degree. C., and still more preferably 25
to 100.degree. C.
[0129] The deposition rate is usually 0.001 nm/sec to 10 nm/sec,
and preferably 0.01 nm/sec to 1 nm/sec. The film thickness of the
organic semiconductor layer formed of the organic material is
usually 1 nm to 10 .mu.m, preferably 5 nm to 5 .mu.m, and more
preferably 10 nm to 3 .mu.m.
[0130] Instead of the deposition method for heating and evaporating
the organic material for forming a semiconductor layer, and
applying the organic material to the substrate, a sputtering method
for colliding accelerated ions of argon or the like against the
target of the material to knock the material atoms out of the
target and applying the material onto the substrate may be
used.
[0131] The semiconductor material in the present invention is an
organic compound, and a relatively low molecular compound.
Accordingly, such a vacuum process can be preferably used. Such a
vacuum process needs a slightly expensive facility, but has
advantages such as excellent film forming properties and easy
formation of a uniform film.
[0132] Meanwhile, the present invention can also use the solution
process, namely, a coating method suitably. The method will be
described. The semiconductor material containing the heterocyclic
compound represented by the compound (1) in the present invention
can be dissolved or dispersed in an organic solvent. Practical
semiconductor properties can be obtained by the solution process.
The production method using a coating method does not need to
provide a vacuum or high temperature environment during production.
For this reason, the production method is advantageous because a
field effect transistor having a large area can be attained at low
cost.
[0133] First, the heterocyclic compound represented by the compound
(1) is dissolved or dispersed in a solvent to prepare an ink for
creating a semiconductor device. The solvent used at this time is
not particularly limited as long as the compound can be dissolved
or dispersed in the solvent to form a film on the substrate. The
solvent is preferably an organic solvent. Specifically,
halogenohydrocarbon solvents such as chloroform, methylene
chloride, and dichloroethane; alcohol solvents such as methanol,
ethanol, isopropyl alcohol, and butanol; fluorinated alcohol
solvents such as octafluoropentanol and pentafluoropropanol; ester
solvents such as ethyl acetate, butyl acetate, ethyl benzoate, and
diethyl carbonate; aromatic hydrocarbon solvents such as toluene,
hexylbenzene, xylene, mesitylene, chlorobenzene, dichlorobenzene,
methoxybenzene, chloronaphthalene, methylnaphthalene, and
tetrahydronaphthalene; ketone solvents such as acetone, methyl
ethyl ketone, methyl isobutyl ketone, cyclopentanone, and
cyclohexanone; amide solvents such as dimethylformamide,
dimethylacetamide, and N-methyl pyrrolidone; ether solvents such as
tetrahydrofuran, diisobutyl ether, diphenyl ether; and hydrocarbon
solvents such as octane, decane, decalin, and cyclohexane can be
used, for example. These can be used singly, or can be used by
mixing.
[0134] For improvement in the film forming properties of the
semiconductor layer or doping described later, for example,
additives and other semiconductor materials can be mixed.
[0135] Examples of these additives include various additives
depending on the function required such as conductive,
semiconductive, and insulative high-molecular compounds and
low-molecular compounds, a dopant, a dispersant, a surfactant, a
leveling agent, and a surface tension adjuster.
[0136] The concentration of the total amount of the heterocyclic
compound represented by the compound (1) or a mixture thereof in
the ink depends on the kind of solvents or the film thickness of
the semiconductor layer to be created, and is usually approximately
0.001% to 50%, and preferably approximately 0.01% to 20%.
[0137] In use of the ink, the semiconductor material containing the
heterocyclic compound represented by the compound (1) or the like
is dissolved or dispersed in the solvent, and a heat dissolution
treatment is performed when necessary. Further, the obtained
solution is filtered using a filter or the like to remove a solid
content such as impurities. Thereby, an ink for creating a
semiconductor device is obtained. Use of such an ink improves the
film forming properties of the semiconductor layer, and is
preferable for creation of the semiconductor layer.
[0138] The thus-prepared ink for creating a semiconductor element
is applied onto the substrate (exposed portions of the insulator
layer, the source electrode, and the drain electrode). For the
application method, coating methods such as casting, spin coating,
dip coating, blade coating, wire bar coating, and spray coating;
printing methods such as inkjet printing, screen printing, offset
printing, and relief printing; a soft lithography method such as a
microcontact printing method; and a method using these in
combination can be used.
[0139] Further, as a method similar to the application method, a
Langmuir-Blodgett method in which a single-molecular film of the
semiconductor layer created by dropping the ink on the surface of
water is transferred onto a substrate and laminated, a method in
which a liquid crystal material or a molten material is sandwiched
by two substrates, and introduced into the gap between the
substrates using a capillary phenomenon, and the like can also be
used.
[0140] The film thickness of the organic semiconductor layer
created by the method is preferably thinner in the range in which
the function is not impaired. A thicker film thickness may cause
larger leakage current. The film thickness of the organic
semiconductor layer is usually 1 nm to 10 .mu.m, preferably 5 nm to
5 .mu.m, and more preferably 10 nm to 3 .mu.m.
[0141] The thus-formed semiconductor layer (see (5) of FIG. 2) can
be subjected to a post treatment to further improve the properties.
For example, the semiconductor properties can be improved or
stabilized by a heat treatment. The reason is thought as follows:
for example, strain in the film caused during film formation is
relaxed by the heat treatment, pin holes and the like reduce, and
arrangement and orientation in the film can be controlled. In
creation of the field effect transistor of the present invention,
the heat treatment is effective in improvement in properties. The
heat treatment is performed by heating the substrate after the
semiconductor layer is formed. The temperature of the heat
treatment is not particularly limited. The temperature is usually
approximately room temperature to 200.degree. C. The heat treatment
time at this time is not particularly limited, and is usually 1
minute to 24 hours. The atmosphere at this time may be in the air,
or may be under an inert atmosphere of nitrogen or argon, for
example.
[0142] As other post treatment methods for the semiconductor layer,
a treatment with an oxidizing or reducing gas such as oxygen and
hydrogen or an oxidizing or reducing liquid can be performed to
induce change in the properties by oxidation or reduction. This
treatment is often used to increase or decrease the carrier density
in the film, for example.
[0143] The properties of the semiconductor layer can be changed
using a method called doping by adding a slight amount of an
element, an atomic group, a molecule, or a polymer to the
semiconductor layer. For example, acids such as oxygen, hydrogen,
hydrochloric acid, sulfuric acid, and sulfonic acid; Lewis acids
such as PF.sub.5, AsF.sub.5, and FeCl.sub.3; halogen atoms such as
iodine; metal atoms such as sodium and potassium; and the like can
be used for doping. The semiconductor layer can be doped by
contacting the semiconductor layer with these gases, immersing the
semiconductor layer in the solution thereof, or performing an
electrochemical doping treatment on the semiconductor layer. Doping
with these dopants may be performed not after creation of the
semiconductor layer. These dopants can be added during synthesis of
the semiconductor material. In the process for creating the
semiconductor layer using the ink for creating a semiconductor
element, these dopants can be added to the ink. Further, these
dopants can be added during the step of forming a precursor thin
film disclosed in Patent Literature 2, for example. A material used
for doping can be added to the material for forming the
semiconductor layer in deposition to perform co-evaporation, or can
be mixed with the ambient atmosphere during creation of the
semiconductor layer (the semiconductor layer is created under the
environment in which a doping material exists). Further, doping can
be performed by accelerating ions in vacuum and colliding the ions
against the film.
[0144] The doping effects are changes in electric conductivity
caused by an increased or decreased carrier density, changes in the
polarity of the carrier (p type, n type), and changes in the Fermi
level, for example. Such doping is often used particularly in the
semiconductor elements using an inorganic material such as
silicon.
(Protective Layer)
[0145] Advantageously, formation of the protective layer 7 on the
organic semiconductor layer can minimize the influence of the
outside air, and stabilize the electrical properties of the organic
field effect transistor (see (6) of FIG. 2). For the protective
layer material, the materials above are used.
[0146] The protective layer 7 can use any film thickness according
to the purpose. The film thickness is usually 100 nm to 1 mm.
[0147] A variety of methods can be used in formation of the
protective layer. When the protective layer is formed of a resin, a
method in which a resin solution is applied and dried to form a
resin film; a method in which a resin monomer is applied or
deposited, and polymerized; and the like can be used, for example.
Further, a crosslinking treatment may be performed after film
formation. When the protective layer is formed of an inorganic
substance, a formation method using a vacuum process such as a
sputtering method and a deposition method, or a formation method
using a solution process such as a sol-gel method can be used, for
example.
[0148] In the field effect transistor of the present invention, the
protective layer can be provided on the organic semiconductor
layer, and when necessary between the layers. These protective
layers may be effective in stabilizing the electrical properties of
the organic field effect transistor.
[0149] The present invention uses the organic material as the
semiconductor material, and enables production by the process at a
relatively low temperature. Consequently, flexible materials such
as plastic plates and plastic films can be used as the substrate
although these flexible materials cannot be used under the high
temperature condition. As a result, the present invention enables
production of an element which is light, highly flexible, and
difficult to break, and such an element can be used as a switching
element of an active matrix for displays, and the like. Examples of
the displays include liquid crystal displays, polymer dispersed
liquid crystal displays, electrophoretic displays, EL displays,
electrochromic displays, and particle rotation displays.
[0150] The field effect transistor of the present invention can
also be used as digital elements such as memory circuit elements,
signal driver circuit elements, signal processing circuit elements
and analog elements. Further, a combination of these enables
creation of IC cards and IC tags. Further, the field effect
transistor of the present invention can change the properties
according to an external stimulus such as a chemical substance, and
therefore can also be used as an FET sensor.
[0151] The operating properties of the field effect transistor are
determined according to the carrier mobility and electric
conductivity of the semiconductor layer, the capacitance of the
insulator layer, the configuration of the element (distance and
width between the source and drain electrodes, the film thickness
of the insulator layer, and the like), and the like. A preferable
semiconductor material used in the field effect transistor is those
having a higher carrier mobility when the semiconductor layer is
formed of the semiconductor material. The heterocyclic compound
represented by the compound (1) in the present invention has
excellent film forming properties. Further, the pentacene
derivative and the like are compound unstable and difficult to
handle because these compounds are decomposed by moisture contained
in the air or the like. When the heterocyclic compound represented
by the compound (1) of the present invention is used as the
semiconductor material, however, the heterocyclic compound
represented by the compound (1) exhibits advantages in that
stability is high and life is long even after creation of the
semiconductor layer. Moreover, the transistor having the
semiconductor layer formed of the heterocyclic compound represented
by the compound (1) has a low threshold voltage. For this reason,
driving voltage reduces in practical use, and power consumption is
smaller than that of the conventional transistor, enabling energy
saving. For example, the transistor of the present invention is
effective in portable displays and the like in which drive for a
longer time is required during using a rechargeable battery.
Moreover, a lower threshold voltage reduces energy consumption.
Further, a lower threshold voltage reduces the barrier against
injection of charges from the electrode to the semiconductor film.
It is expected that such a lower threshold voltage also is
effective in improving the durability of the semiconductor element
and the semiconductor device itself having the semiconductor
element.
EXAMPLES
[0152] Hereinafter, the present invention will be more specifically
described using Examples, but the present invention will not be
limited to these examples. In Examples, "parts" indicate "parts by
mass" and "%" indicates "% by mass" unless otherwise specified. The
reaction temperatures described in Examples are inner temperature
of reaction systems unless otherwise specified.
[0153] The formulas of a variety of compounds obtained in Synthesis
Examples were determined when necessary by performing a variety of
measurements of mp (melting point), NMR (1H, 13C), IR (infrared
absorption spectrum), MS (mass spectrometry spectrum), and element
analysis. The measurement apparatuses are shown below.
[0154] mp: Yanagimoto micro melting point measurement apparatus
MP-S3
[0155] NMR: JEOL Lambda 400 spectrometer
[0156] IR: SHIMADZU Fourier transform infrared spectrophotometer IR
Prestige-21
[0157] MS spectrum: Shimadzu QP-5050A
[0158] element analysis: Parkin Elmer 2400CHN element analyzer
[0159] First, synthesis of compounds will be specifically
described.
Example 1
Synthesis of 6-n-decyl-2-methoxynaphthalene compound (compound
(3)-64)
Example 1-1
Synthesis of 2-decanoyl-6-methoxynaphthalene
[0160] Under a nitrogen atmosphere, 2-methoxynaphthalene (64 g,
0.41 mol) easily available from a reagent manufacturer was
dissolved in nitromethane (150 ml) dried with a molecular sieve 3A.
Under an ice bath, aluminum chloride (80 g, 0.60 mol) was added.
Subsequently, decanoyl chloride (92 ml, 0.45 mol) was dropped into
the solution under the ice bath. The solution was stiffed under
room temperature for 5 hours, and water (100 ml) was dropped into
the solution under the ice bath. The reaction solution was
extracted with methylene chloride (200 ml.times.4), and the
obtained organic layer was washed with water (100 ml.times.3). The
organic layer was dried with anhydrous magnesium sulfate, and
filtered. Then, the solvent was distilled away under reduced
pressure. The obtained yellow solid was recrystallized from hexane
to obtain 2-decanoyl-6-methoxynaphthalene (102 g, 82%) as a white
solid.
[0161] .sup.1H-NMR (270 MHz, CDCl.sub.3) .delta. 0.88 (t, 2H, J=6.5
Hz), 1.18-1.49 (br, 16H), 1.78 (m, 2H), 3.07 (t, 2H, J=7.4 Hz),
3.95 (s, 3H), 7.16 (d, 1H, J=2.6 Hz), 7.20 (dd, 1H, J=8.9 Hz, 2.3
Hz), 7.77 (d, 1H, J=8.6 Hz), 7.86 (d, 1H, J=8.9 Hz), 8.01 (dd, 1H,
J=8.6 Hz, 1.6 Hz), 8.40 (s, 1H); EIMS (70 eV) m/z=312 (M.sup.+)
Example 1-2
Synthesis of 6-n-decyl-2-hydroxynaphthalene
##STR00019##
[0163] Under a nitrogen atmosphere, 2-decanoyl-6-methoxynaphthalene
(9.4 g, 30 mmol) and potassium hydroxide (67 g, 1.2 mol) were
dissolved in hydrazine monohydrate (70 ml, 1.4 mol) and diethylene
glycol (200 ml). The solution was refluxed for 17 hours, and water
(36 ml) was added. Under a stream of nitrogen, the solution was
distilled to distill away an excessive amount of hydrazine and
water. Further, the solution was refluxed under a nitrogen
atmosphere for 41 hours. Subsequently, while using an ice bath, the
solution was cooled by putting ice into the reaction solution,
hydrochloric acid was slowly added until the solution became
neutral. The reaction solution was extracted with ether (100
ml.times.3), and the obtained organic layer was washed with
saturated saline water (100 ml.times.5). The organic layer was
dried with anhydrous magnesium sulfate, and filtered. Then, the
solvent was distilled away under reduced pressure. The obtained
brown solid was recrystallized from hexane to obtain
6-decyl-2-hydroxynaphthalene (7.3 g, 90%) as a white solid.
[0164] .sup.1H-NMR (270 MHz, CDCl.sub.3) .delta. 0.88 (t, 2H, J=6.5
Hz), 1.18-1.43 (br, 17H), 1.59-1.75 (br, 3H), 2.72 (t, 2H, J=7.7
Hz), 4.99 (s, 1H), 7.07 (dd, 1H, J=8.9 Hz, 2.6 Hz), 7.11 (d, J=2.3
Hz), 7.28 (dd, 1H, J=8.4 Hz, 1.8 Hz), 7.53 (br, 1H), 7.60 (d, 1H,
J=8.6 Hz), 7.68 (d, 1H, J=8.9 Hz); EIMS (70 eV) m/z=284
(M.sup.+)
Example 1-3
Synthesis of 6-n-decyl-2-methoxynaphthalene (compound (3)-64)
##STR00020##
[0166] Under a nitrogen atmosphere, 6-n-decyl-2-hydroxynaphthalene
(5.68 g, 20 mmol) and a THF (200 ml) solution of 55% NaH (oil
dispersion, 880 mg, 20 mmol) were stiffed at room temperature for
40 minutes. CH.sub.3I (1.48 ml, 24 mmol) was added to the mixed
solution, and the mixed solution was heated under reflux for 12
hours. Water (20 ml) was added to the mixture at 0.degree. C., and
the mixture was washed with saline water. Organic layers were
combined, and dried with MgSO.sub.4, and condensed with an
evaporator. The condensed solution was recrystallized from methanol
to obtain 6-n-decyl-2-methoxynaphthalene (compound (3)-64) (5.0 g,
85%) as a white solid.
[0167] .sup.1H-NMR (270 MHz, CDCl.sub.3) .delta. 0.88-1.70
(aliphatic), 2.72 (t, 2H, J=7.2 Hz), 3.90 (s, 3H), 7.09-7.13 (m,
2H,), 7.29 (dd, 1H, J=8.2 Hz, 1.6 Hz), 7.53 (br, 1H), 7.64 (d, 1H,
J=2.0 Hz), 7.68 (d, 1H, J=3.3 Hz); EIMS (70 eV) m/z=298
(M.sup.+)
Example 2
Synthesis of 6-n-decyl-2-methoxynaphthalene (compound (3)-64) by
another method
##STR00021##
[0169] A THF solution of n-decyl magnesium bromide (prepared as a
THF (2 ml) solution of n-decyl bromide (2.2 ml, 11 mmol) and Mg
(292 mg, 12 mmol)) was added to 6-bromo-2-methoxynaphthalene (2.37
g, 10 mmol) easily available from a reagent manufacturer and a THF
(10 ml) solution of Ni(dppp)Cl.sub.2 (271 mg, 0.5 mmol), and the
mixture was heated under reflux for 19 hours. After cooling, the
mixed solution was diluted with water (10 ml), and non-reacted Mg
was filtered out. The filtered solution was extracted with ether (5
ml.times.3). The extracted organic phases were collected (10
ml.times.3), and dried with MgSO.sub.4, and condensed with an
evaporator. The condensed organic phase was recrystallized with
hexane to obtain 6-n-decyl-2-methoxynaphthalene (compound (3)-64)
as a light yellow solid.
[0170] mp 48.6 to 49.3.degree. C.; .sup.1H NMR (270 MHz,
CDCl.sub.3) .delta. 0.87 (t, J=6.7 Hz, 3H), 1.25-1.32 (m, 14H),
1.67 (quint, J=7.7 Hz, 2H), 2.72 (t, J=7.2 Hz, 2H), 3.90 (s, 3H),
7.09-7.13 (m, 2H), 7.29 (dd, J=8.2 Hz, 1.6 Hz, 1H), 7.53 (brs, 1H),
7.64 (d, J=2.0 Hz, 1H), 7.68 (d, J=3.3 Hz, 1H); .sup.13C NMR (100
MHz, CDCl.sub.3); .delta. 14.1, 22.7, 29.4, 29.6 (.times.3), 31.5,
31.9, 35.9, 55.2, 105.6, 118.5, 126.1, 126.0, 127.9, 128.9, 129.1,
132.9, 138.1, 157.0; EIMS (70 eV) m/z=298 (M.sup.+); Anal. Calcd
for C.sub.21H.sub.30O: C, 84.51; H, 10.13%. Found: C, 84.62; H,
10.41%.
Example 3
Synthesis of 7-decyl-2-methoxynaphthalene (compound (3)-12)
##STR00022##
[0172] 1-Decyne (1.2 g, 6.5 mmol), PdCl.sub.2(PPh.sub.3).sub.2
(0.12 g, 0.16 mmol), CuI (13 mg, 0.065 mmol), and triethylamine (14
ml, 9.8 mmol) were added to a THF (20 ml) solution of
7-methoxy-2-naphthyltrifluoromethane sulfonate (1.0 g, 3.3 mmol).
The solution was mixed at room temperature for 4 hours, and diluted
with water (30 ml). The solution was made acidic with diluted
hydrochloric acid (2 M), and extracted with dichloromethane (30
ml.times.3). The extracted solution was washed with water (100
ml.times.3), and dried with MgSO.sub.4. The solution was condensed,
and subjected to column chromatography (silica gel, developed with
dichloromethane) to obtain 7-decyn-1-yl-2-methoxynaphthalene as a
light yellow oil product. The obtained
7-decyn-1-yl-2-methoxynaphthalene (2.8 mmol) and a THF (13 ml) of
10% Pd/C (0.16 g) were placed in a 50 ml round-bottomed flask.
Under a hydrogen atmosphere, the solution was stirred until the
reaction was completed (approximately 12 hours) while the reaction
was tracked using TLC. When the reaction was completed, a catalyst
was filtered out, and the filtrate was condensed. The condensed
solution was refined by column chromatography (silica gel,
developed with dichloromethane) to obtain
7-decyl-2-methoxynaphthalene (compound (3)-12) (0.80 g, 82%).
[0173] mp 29.9 to 30.8.degree. C.; .sup.1H NMR (270 MHz,
CDCl.sub.3) .delta. 0.88 (t, J=7.0 Hz, 3H), 1.27-1.171 (m, 16H),
2.74 (t, J=7.7 Hz, 2H), 3.92 (s, 3H), 7.07 (dd, J=9.7, 2.4 Hz, 1H),
7.09 (s, 1H), 7.19 (dd, J=8.3, 1.7 Hz, 1H), 7.51 (s, 1H), 7.68 (d,
J=8.3 Hz, 1H), 7.70 (d, J=9.7 Hz, 1H); .sup.13C NMR (100 MHz,
CDCl.sub.3); .delta. 14.4, 23.0, 29.6, 29.7, 29.9, 30.2 (.times.2),
31.7, 32.3, 36.5, 55.6, 105.8, 118.1, 125.6, 125.7, 127.8
(.times.2), 129.4, 135.1, 141.4, 158.0; EIMS (70 eV) m/z=298
(M.sup.+); Anal. Calcd for C.sub.21H.sub.30O: C, 84.51; H, 10.13%.
Found: C, 84.48; H, 10.44%.
Example 4
Synthesis of 7-phenyl-2-methoxynaphthalene (compound (3)-22)
[0174] n-Hydrate of potassium phosphate (34 g, 0.16 mol) and
phenylboric acid (3.7 g, 30 mmol) were added to a DMF (350 ml)
solution of 7-methoxy-2-naphthyltrifluoromethane sulfonate (6.1 g,
20 mmol). The solution was bubbled with nitrogen for 30 minutes to
perform replacement with nitrogen. PdCl.sub.2(PPh).sub.2 (0.71 g, 1
mmol) was added, and the solution was heated for 4 hours at
80.degree. C. A saturated ammonium chloride aqueous solution (500
ml) was added to the obtained mixture. Crystals deposited by this
operation was filtered out, washed with water (100 ml.times.3), and
dried with an electric dryer (60.degree. C.). The crude product was
refined by column chromatography (silica gel, developed with
dichloromethane) to obtain 7-phenyl-2-methoxynaphthalene (compound
(3)-22), 3.4 g).
[0175] yield of 73%; yellow crystal (recrystallized with
hexane);
[0176] mp 65.4 to 66.3.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 3.95 (s, 3H), 7.15 (dd, J=8.9, 2.5 Hz, 1H),
7.38 (tt, J=7.4, 1.2 Hz, 1H), 7.46-7.50 (m, 2H), 7.60 (dd, J=8.5,
1.6 Hz, 1H), 7.70-7.72 (m, 2H), 7.76 (d, J=8.9 Hz, 1H), 7.84 (d,
J=8.5 Hz, 1H), 7.95 (d, J=1.6 Hz, 1H); .sup.13C NMR (100 MHz,
CDCl.sub.3) .delta. 55.7, 106.5, 119.1, 123.7, 125.1, 127.7, 127.8,
128.5 .cndot.(.times.2), 129.2, 129.5, 135.2, 139.5, 141.7, 158.4;
EI-MS, m/z=234 (M.sup.+); Anal. Calcd for C.sub.17H.sub.14O: C,
87.15; H, 6.02%. Found: C, 87.23; H, 6.03%.
Example 5
Synthesis of 6-phenyl-2-methoxynaphthalene (compound (3)-31)
[0177] A target product 6-phenyl-2-methoxynaphthalene (compound
(3)-31) was obtained at a yield of 90% from
6-bromo-2-methoxynaphthalene (easily available from a reagent
manufacturer) and phenylboric acid by the same operation as that in
the method for synthesizing 7-phenyl-2-methoxynaphthalene according
to Example 4.
[0178] mp 135.4 to 136.4.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 3.95 (s, 3H), 7.17 (s, 1H), 7.19 (dd, J=7.9,
2.5 Hz, 1H), 7.38 (tt, J=7.4, 1.2 Hz, 1H), 7.45-7.49 (m, 2H), 7.72
(dd, J=8.5, 1.8 Hz, 1H), 7.70-7.72 (m, 2H), 7.80 (d, J=7.9 Hz, 1H),
7.82 (d, J=7.9 Hz, 1H), 7.98 (d, J=1.8 Hz, 1H); EI-MS, m/z=234
(M.sup.+); Anal. Calcd for C.sub.17H.sub.14O: C, 87.15; H, 6.02%.
Found: C, 86.86; H, 5.94%
Example 6
Synthesis of 6-tolyl-2-methoxynaphthalene (compound (3)-32)
[0179] 6-Tolyl-2-methoxynaphthalene (compound (3)-32, 33.3 g, yield
of 82%) was obtained by the same operation as that in the method
for synthesizing 7-phenyl-2-methoxynaphthalene according to Example
4 except that 6-bromo-2-methoxynaphthalene (38.9 g, 0.16 mol) was
used instead of 7-methoxy-2-naphthyltrifluoromethane sulfonate and
4-methylphenylboric acid (25.0 g, 0.21 mol) was used instead of
4-phenylboric acid.
[0180] EI-MS, m/z=248 (M.sup.+)
Example 7
Synthesis of 7-tolyl-2-methoxynaphthalene (compound (3)-23)
[0181] 7-Tolyl-2-methoxynaphthalene (compound (3)-23, 22.5 g, yield
of 96%) was obtained using 7-methoxy-2-naphthyltrifluoromethane
sulfonate (30.63 g, 0.10 mol) and 4-methylphenylboric acid (16.12
g, 0.12 mol) by the same operation as that in the method for
synthesizing 7-phenyl-2-methoxynaphthalene according to Example
4.
[0182] EI-MS, m/z=248 (M.sup.+)
Example 8
Synthesis of 6-biphenyl-2-methoxynaphthalene (compound (3)-33)
[0183] 6-Biphenyl-2-methoxynaphthalene (compound (3)-33, 24.8 g,
yield of 84%) was obtained by the same operation as that in the
method for synthesizing 7-phenyl-2-methoxynaphthalene according to
Example 4 except that 6-bromo-2-methoxynaphthalene (22.5 g, 94.8
mmol) was used instead of 7-methoxy-2-naphthyltrifluoromethane
sulfonate and 4-biphenylboric acid (23.48 g, 119 mmol) was
used.
[0184] EI-MS, m/z=310 (M.sup.+)
Example 9
Synthesis of 7-biphenyl-2-methoxynaphthalene (compound (3)-24)
[0185] 7-Biphenyl-2-methoxynaphthalene (compound (3)-24, 21.9 g,
yield of 74%) was synthesized by the same operation as that in the
method for synthesizing 7-phenyl-2-methoxynaphthalene according to
Example 4 using 7-methoxy-2-naphthyltrifluoromethane sulfonate
(29.05 g, 94.8 mmol) and 4-biphenylboric acid (23.48 g, 119
mmol).
[0186] EI-MS, m/z=310 (M.sup.+)
Example 10
Synthesis of 7-butyl-2-methoxynaphthalene (compound (3)-04)
[0187] Using 7-methoxy-2-naphthyltrifluoromethanesulfonate (30.63
g, 0.10 mol) and butyne gas (a product manufactured by TOKYO
CHEMICAL INDUSTRY CO., LTD., 100 g, large excess),
7-butyn-1-yl-2-methoxynaphthalene was synthesized by the same
operation as that in the method for synthesizing
7-decyl-2-methoxynaphthalene according to Example 3, and subjected
to column chromatography (silica gel, developed with a mixture of
toluene and hexane) to obtain a light yellow oil product of
7-butyn-1-yl-2-methoxynaphthalene (18.1 g, yield of 56%). The
obtained 7-butyn-1-yl-2-methoxynaphthalene (total amount) was
subjected to catalytic reduction in toluene (275 ml) under a
hydrogen atmosphere by adding 10% Pd/C (1.83 g). The obtained
product was subjected to column chromatography (silica gel,
developed with a mixture of toluene and hexane) to obtain
7-butyl-2-methoxynaphthalene (compound (3)-04, 17.80 g, yield of
97%).
[0188] EI-MS, m/z=214 (M.sup.+)
Example 11
Synthesis of 7-hexyl-2-methoxynaphthalene (compound (3)-08)
[0189] Using 7-methoxy-2-naphthyltrifluoromethanesulfonate (30.63
g, 0.10 mol) and 1-hexyne (10.27 g, 0.125 mol),
7-hexyn-1-yl-2-methoxynaphthalene was synthesized by the same
operation as that in the method for synthesizing
7-decyl-2-methoxynaphthalene according to Example 3, and subjected
to column chromatography (silica gel, developed with a mixture of
toluene and hexane) to obtain a light yellow oil product of
7-hexyn-1-yl-2-methoxynaphthalene (20.5 g, yield of 86%). The
obtained 7-hexyn-1-yl-2-methoxynaphthalene (total amount) was
subjected to catalytic reduction in toluene (275 ml) under a
hydrogen atmosphere by adding 10% Pd/C (1.83 g). The obtained
product was subjected to column chromatography (silica gel,
developed with a mixture of toluene and hexane) to obtain
7-hexyl-2-methoxynaphthalene (compound (3)-08, 20.70 g, yield of
99%).
[0190] EI-MS, m/z=242 (M.sup.+)
Example 12
Synthesis of 7-octyl-2-methoxynaphthalene (compound (3)-10)
[0191] Using 7-methoxy-2-naphthyltrifluoromethanesulfonate (30.63
g, 0.10 mol) and 1-octyne (13.78 g, 0.125 mol),
7-octyn-1-yl-2-methoxynaphthalene was synthesized by the same
operation as that in the method for synthesizing
7-decyl-2-methoxynaphthalene according to Example 3, and subjected
to column chromatography (silica gel, developed with a mixture of
toluene and hexane) to obtain a light yellow oil product of
7-octyn-1-yl-2-methoxynaphthalene (22.9 g, yield of 86%). The
obtained 7-octyn-1-yl-2-methoxynaphthalene (total amount) was
subjected to catalytic reduction in toluene (213 ml) under a
hydrogen atmosphere by adding 10% Pd/C (2.13 g). The obtained
product was subjected to column chromatography (silica gel,
developed with a mixture of toluene and hexane) to obtain
7-octyl-2-methoxynaphthalene (compound (3)-10, 24.30 g, yield of
90%).
[0192] EI-MS, m/z=270 (M.sup.+)
Example 13
Synthesis of 7-dodecyl-2-methoxynaphthalene (compound (3)-14)
[0193] Using 7-methoxy-2-naphthyltrifluoromethanesulfonate (30.63
g, 0.10 mol) and 1-dodecyne (20.79 g, 0.125 mol),
7-dodecyn-1-yl-2-methoxynaphthalene was synthesized by the same
operation as that in the method for synthesizing
7-decyl-2-methoxynaphthalene according to Example 3, and subjected
to column chromatography (silica gel, developed with a mixture of
toluene and hexane) to obtain a light yellow oil product of
7-dodecyn-1-yl-2-methoxynaphthalene (32.0 g, quantitative). The
obtained 7-dodecyn-1-yl-2-methoxynaphthalene (total amount) was
subjected to catalytic reduction in toluene (316 ml) under a
hydrogen atmosphere by adding 10% Pd/C (2.11 g). The obtained
product was subjected to column chromatography (silica gel,
developed with a mixture of toluene and hexane) to obtain
7-dodecyl-2-methoxynaphthalene (compound (3)-14, 31.10 g, yield of
96%).
[0194] EI-MS, m/z=326 (M.sup.+)
[0195] Examples in which the compound (4) was derived from the
compound (3) will be shown below.
Example 14
Synthesis of 6-n-decyl-3-methylthio-2-methoxynaphthalene (compound
(4)-64)
[0196] A hexane solution of 1.57 Mn--BuLi (28 ml, 44 mmol) was
added to a THF (100 ml) solution of 6-n-decyl-2-methoxynaphthalene
(compound (3)-64) (12 g, 40 mmol) at -78.degree. C., and the
solution was stirred at room temperature for 1 hour. Dimethyl
disulfide (4.4 ml, 48 mmol) was added to the solution at
-78.degree. C., and the solution was stirred at room temperature
for 18 hours. The reaction solution was added to a saturated
ammonium chloride aqueous solution (50 ml), and extracted with
ether (30 ml.times.3). The extracted solutions obtained by
repeating the extraction 3 times were collected, washed with a
saturated saline water (30 ml.times.3), and dried with MgSO.sub.4.
The dried product was condensed with an evaporator to obtain
6-n-decyl-3-methylthio-2-methoxynaphthalene (compound (4)-64) (15.2
g, quantitative) as a yellow oil. The compound can be used in the
subsequent reaction without performing further refining.
[0197] .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 0.87 (t, J=6.7 Hz,
3H), 1.25-1.32 (m, 14H), 1.67 (quint, J=7.7 Hz, 2H), 2.72 (t, J=7.2
Hz, 2H), 2.53 (s, 3H), 2.72 (t, J=7.8 Hz, 2H), 3.98 (s, 3H), 7.05
(s, 1H), 7.23 (d, J=6.8 Hz, 1H), 7.40 (s, 1H), 7.48 (s, 1H), 7.62
(d, J=8.8 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3); .delta.
14.1, 14.6, 22.7, 29.4, 29.6 (.times.3), 31.5, 31.9, 36.0, 55.8,
104.6, 122.9, 125.0, 126.3, 127.0, 129.4, 130.4, 138.7, 154.0; EIMS
(70 eV) m/z=344 (M.sup.+). Anal Calcd for C.sub.22H.sub.32OS: C,
76.69; H, 9.36%. Found: C, 76.83; H, 9.66%.
Example 15
Synthesis of 7-decyl-3-methylthio-2-methoxynaphthalene (compound
(4)-12)
[0198] 7-Decyl-3-methylthio-2-methoxynaphthalene (compound (4)-12)
was synthesized from 7-decyl-2-methoxynaphthalene (compound (3)-12)
and dimethyl disulfide by the same method as that in Example 14
(yield of 93%, recrystallized from hexane to obtain yellow
crystals).
[0199] mp 49.5 to 50.4.degree. C.; .sup.1H NMR (500 MHz,
CDCl.sub.3) .delta. 0.87 (t, J=6.8 Hz, 3H), 1.24-1.69 (m, 16H),
2.53 (s, 3H), 2.72 (t, J=7.8 Hz, 2H), 3.99 (s, 3H), 7.03 (s, 1H),
7.18 (d, J=8.4 Hz, 1H), 7.44 (s, 1H), 7.48 (s, 1H), 7.62 (d, J=8.4
Hz, 1H); .sup.13CNMR (126 MHz, CDCl.sub.3); .delta. 14.5, 15.1,
23.0, 29.7 (.times.2), 29.9 (.times.2), 30.0, 31.7, 32.2, 36.4
56.2, 104.8, 123.7, 125.4, 126.0, 126.6, 128.0, 128.6, 132.7,
140.6, 155.0; EIMS (70 eV) m/z=344 (M.sup.+). Anal Calcd for
C.sub.22H.sub.32OS: C, 76.69; H, 9.36%. Found: C, 76.83; H,
9.66%.
Example 16
3-methylthio-7-phenyl-2-methoxynaphthalene (compound (4)-22)
[0200] 3-Methylthio-7-phenyl-2-methoxynaphthalene (compound (4)-22)
was obtained by the same method as that in Example 14 from
7-phenyl-2-methoxynaphthalene (compound (3)-22) and dimethyl
disulfide at a yield of 77% (recrystallized from hexane to obtain
yellow crystals).
[0201] mp 149 to 150.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 2.56 (s, 3H), 4.03 (s, 3H), 7.15 (s, 1H), 7.38 (tt, J=7.4,
1.3 Hz, 1H), 7.46-7.49 (m, 2H), 7.47 (s, 1H), 7.61 (dd, J=8.4, 1.8
Hz, 1H), 7.70-7.72 (m, 2H), 7.77 (d, J=8.5 Hz, 1H), 7.92 (d, J=1.8
Hz, 1H); EI-MS, m/z=280 (M.sup.+); Anal. Calcd for
C.sub.18H.sub.16OS: C, 77.11; H, 5.75%. Found: C, 77.05; H,
5.64%.
Example 17
Synthesis of 3-methylthio-6-phenyl-2-methoxynaphthalene (compound
(4)-31)
[0202] 3-Methylthio-6-phenyl-2-methoxynaphthalene (compound (4)-31)
was synthesized from 6-phenyl-2-methoxynaphthalene (compound
(3)-31) and dimethyl disulfide by the same method as that in
Example 14.
[0203] mp 124 to 125.2.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 2.56 (s, 3H), 4.02 (s, 3H), 7.11 (s, 1H), 7.36
(tt, J=7.4, 1.3 Hz, 1H), 7.45-7.50 (m, 2H), 7.53 (s, 1H), 7.66 (dd,
J=8.5, 1.6 Hz, 1H), 7.69-7.72 (m, 2H), 7.77 (d, J=8.5 Hz, 1H), 7.92
(d, J=1.6 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3) .delta. 14.9,
56.3, 104.8, 123.7, 124.8, 125.4, 127.3, 127.4, 127.6, 129.2,
129.9, 130.6, 131.6, 137.2, 141.6; EI-MS, m/z=280 (M.sup.+); Anal.
Calcd for C.sub.18H.sub.16OS: C, 77.11; H, 5.75%. Found: C, 77.22;
H, 5.75%.
Example 18
Synthesis of 6-tolyl-3-methylthio-2-methoxynaphthalene (compound
(4)-32)
[0204] 6-Tolyl-3-methylthio-2-methoxynaphthalene (compound (4)-32,
19.22 g, 49%) was obtained from 6-tolyl-2-methoxynaphthalene
(compound (3)-32, 33.3 g) and dimethyl disulfide by the same method
as that in Example 14. The process can go to the subsequent
reaction without performing further refining.
[0205] EI-MS, m/z=294 (M.sup.+)
Example 19
Synthesis of 7-tolyl-3-methylthio-2-methoxynaphthalene (compound
(4)-23)
[0206] 7-Tolyl-3-methylthio-2-methoxynaphthalene was synthesized
from 7-tolyl-2-methoxynaphthalene (compound (3)-23, 22.2 g, 89
mmol) by the same method as that in Example 14, and recrystallized
from toluene to obtain a compound (compound (4)-23, 11.5 g, yield
of 44%). The process can go to the subsequent reaction without
performing further refining.
[0207] EI-MS, m/z=294 (M.sup.+)
Example 20
Synthesis of 6-biphenyl-3-methylthio-2-methoxynaphthalene (compound
(4)-33)
[0208] 6-Biphenyl-3-methylthio-2-methoxynaphthalene (compound
(4)-33, 22.3 g, 81%) was obtained from
6-biphenyl-2-methoxynaphthalene (compound (3)-33, 24.0 g) by the
same method as that in Example 14. The process can go to the
subsequent reaction without performing further refining.
[0209] EI-MS, m/z=356 (M.sup.+)
Example 21
Synthesis of 7-biphenyl-3-methylthio-2-methoxynaphthalene (compound
(4)-24)
[0210] 7-Biphenyl-3-methylthio-2-methoxynaphthalene (compound
(4)-24) was synthesized from 7-biphenyl-2-methoxynaphthalene
(compound (3)-24, 21.5 g) by the same method as that in Example 14,
and recrystallized from toluene to obtain a compound (4)-24 (16.0
g, yield of 65%). The process can go to the subsequent reaction
without performing further refining.
[0211] EI-MS, m/z=356 (M.sup.+)
Example 22
Synthesis of 7-butyl-3-methylthio-2-methoxynaphthalene (compound
(4)-04)
[0212] 7-Butyl-3-methylthio-2-methoxynaphthalene (compound (4)-04,
22.3 g, yield of 100%) was obtained from
7-butyl-2-methoxynaphthalene (compound (3)-04, 17.80 g, 83.1 mmol)
by the same method as that in Example 14. The process can go to the
subsequent reaction without performing further refining.
[0213] EI-MS, m/z=260 (M.sup.+)
Example 23
Synthesis of 7-hexyl-3-methylthio-2-methoxynaphthalene (compound
(4)-08)
[0214] 7-Hexyl-3-methylthio-2-methoxynaphthalene (compound (4)-08,
24.7 g, quantitative) was obtained from
7-hexyl-2-methoxynaphthalene (compound (3)-08) by the same method
as that in Example 14. The process can go to the subsequent
reaction without performing further refining.
[0215] EI-MS, m/z=288 (M.sup.+)
Example 24
Synthesis of 7-octyl-3-methylthio-2-methoxynaphthalene (compound
(4)-10)
[0216] 7-Octyl-3-methylthio-2-methoxynaphthalene (compound (4)-10,
27.09 g, yield of 95%) was obtained from
7-octyl-2-methoxynaphthalene (compound (3)-10) by the same method
as that in Example 14. The process can go to the subsequent
reaction without performing further refining.
[0217] EI-MS, m/z=316 (M.sup.+)
Example 25
Synthesis of 7-dodecyl-3-methylthio-2-methoxynaphthalene (compound
(4)-14)
[0218] 7-Dodecyl-3-methylthio-2-methoxynaphthalene (compound
(4)-14, 34.1 g, yield of 96%) was obtained from
7-dodecyl-2-methoxynaphthalene (compound (3)-14) by the same method
as that in Example 14. The process can go to the subsequent
reaction without performing further refining.
[0219] EI-MS, m/z=372 (M.sup.+)
[0220] The following operation can perform on the substituent in
the compound (4) to easily convert the compound (4) to a derivative
having another substituent.
Synthesis Example 1
Synthesis of
6-decyl-3-methylthio-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-81)
Synthesis Example 1-1
Synthesis of 6-decyl-3-methylthio-2-hydroxynaphthalene
##STR00023##
[0222] A dichloromethane (50 ml) solution of
6-decyl-3-methylthio-2-methoxynaphthalene (compound (4)-64) (28 g,
81 mmol) was added to a dichloromethane solution of BBr.sub.3 (ca.2
M 70 ml, 140 mmol) at -78.degree. C. The solution was stirred at
room temperature for 12 hours. Ice (approximately 20 g) was added
to the mixture. The reaction solution was extracted with
dichloromethane (20 ml.times.3). The organic layers obtained by
repeating the extraction three times were collected, washed with
saturated saline water (30 ml.times.3), dried with MgSO.sub.4, and
condensed. The residue was refined by column chromatography (silica
gel, developed at dichloromethane:hexane=1:1), and recrystallized
with hexane to obtain 6-decyl-3-methylthio-2-hydroxynaphthalene
(18.1 g, 72%) as white crystals.
[0223] mp 65.5 to 66.0.degree. C.; .sup.1H NMR (270 MHz,
CDCl.sub.3) .delta. 0.88 (t, J=6.7 Hz, 3H), 1.26-1.32 (m, 14H),
1.67 (quint, J=7.7 Hz, 2H), 2.41 (s, 3H), 2.71 (t, J=7.3 Hz, 2H),
6.57 (s, 1H), 7.28 (s, 1H), 7.28 (dd, J=8.2 Hz, 1.6 Hz, 1H), 7.48
(brs, 1H), 7.61 (d, J=8.6 Hz, 1H), 7.94 (s, 1H); .sup.13C NMR (100
MHz, CDCl.sub.3) .delta. 14.1, 19.9, 22.7, 29.3, 29.6 (.times.3),
31.4, 31.9, 35.9, 109.1, 124.1, 125.7, 126.3, 128.7, 129.1, 133.5
(.times.2), 138.5, 152.1; IR (KBr) .nu. 3402 cm.sup.-1 (OH); EIMS
(70 eV) m/z=330 (M.sup.+); Anal. Calcd for C.sub.21H.sub.30OS: C,
76.31; H, 9.15%. Found: C, 76.34; H, 9.23%.
Synthesis Example 1-2
Synthesis of
6-decyl-3-methylthio-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-81)
##STR00024##
[0225] Trifluoromethanesulfonic anhydride (3 ml, 15 mmol) was added
to a dichloromethane (50 ml) solution of the obtained
6-decyl-3-methylthio-2-hydroxynaphthalene (3.63 g, 10 mmol) and
pyridine (2.5 ml, 30 mmol) at 0.degree. C. This solution was
stirred at room temperature for 25 minutes. Then, the mixture was
diluted with water (20 ml), and hydrochloric acid (4 M, 20 ml) was
added. The mixture was extracted with dichloromethane (30
ml.times.3). The organic phases obtained by repeating the
extraction three times were collected, washed with saturated saline
water (30 ml.times.3), dried with MgSO.sub.4, and condensed to
obtain
6-decyl-3-methylthio-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-81) (4.89 g, 99%).
[0226] mp 42.0 to 42.9.degree. C.; .sup.1H NMR (270 MHz,
CDCl.sub.3) .delta. 0.88 (t, J=6.7 Hz, 3H), 1.26-1.32 (m, 14H),
1.68 (quint, J=7.7 Hz, 2H), 2.59 (s, 3H), 2.76 (t, J=7.3 Hz, 2H),
7.36 (dd, J=8.7 Hz, 1.8 Hz, 1H), 7.57 (brs, 1H), 7.63 (s, 1H), 7.68
(s, 1H), 7.72 (d, J=8.2 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3)
.delta. 14.1, 15.8, 22.7, 29.3 (.times.2), 29.5, 29.6 (.times.2),
31.2, 31.9, 36.1, 118.7 (q, J=319 Hz), 119.2, 125.2, 126.3, 127.7,
128.4, 129.4, 130.7, 133.0, 142.7, 144.8; IR (KBr) .nu. 1423, 1211
cm.sup.-1 (--O--SO.sub.2--); EIMS (70 eV) m/z=462 (M.sup.+); Anal.
Calcd for C.sub.22H.sub.29F.sub.3O.sub.3S.sub.2: C, 57.12; H,
6.32%. Found C, 56.91; H, 6.15%.
Synthesis Example 2
Synthesis of
7-decyl-3-methylthio-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-77)
Synthesis Example 2-1
Synthesis of 7-decyl-3-methylthio-2-hydroxynaphthalene
[0227] 7-Decyl-3-methylthio-2-methoxynaphthalene (compound (4)-12)
synthesized in Example 15 was demethylated by the operation in
(Synthesis Example 1-1) to obtain
7-decyl-3-methylthio-2-hydroxynaphthalene.
[0228] yield of 85%; yellow crystal (recrystallized with
hexane);
[0229] mp 64.4 to 65.4.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 0.88 (t, J=6.9 Hz, 3H), 1.24-1.72 (m, 16H),
2.40 (s, 3H), 2.72 (t, J=7.7 Hz, 2H), 6.63 (s, 1H), 7.17 (dd,
J=8.4, 1.6 Hz, 1H), 7.45 (s, 1H), 7.63 (d, J=8.4 Hz, 1H), 7.97 (s,
1H); .sup.13C NMR (100 MHz, CDCl.sub.3) .delta. 14.4, 20.4, 23.0,
29.6, 29.7, 29.9 (.times.2), 31.6, 32.2, 36.5, 109.1, 123.4, 125.2,
125.9, 127.5, 127.8, 134.5, 135.8, 142.3, 153.2; IR (KBr) .nu. 3402
cm.sup.-1 (OH); EI-MS, m/z=330 (M.sup.+); Anal. Calcd for
C.sub.21H.sub.30OS: C, 76.31; H, 9.15%. Found: C, 76.62; H,
9.38%.
Synthesis Example 2-2
Synthesis of
7-decyl-3-methylthio-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-77)
[0230] 7-Decyl-3-methylthio-2-hydroxynaphthalene was
trifluoromethanesulfonylated by the same operation as that in
(Synthesis Example 1-2) to obtain
7-decyl-3-methylthio-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-77).
[0231] yield of 94%; yellow crystal (recrystallized with
hexane);
[0232] mp 149 to 150.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 2.44 (s, 3H), 6.64 (s, 1H), 7.38-7.40 (m, 2H), 7.48 (tt,
J=7.6, 1.8 Hz, 1H), 7.60 (d, J=8.5 Hz, 1H), 7.70-7.72 (m, 2H), 7.80
(dd, J=8.5, 2.0 Hz, 1H), 7.88 (s, 1H), 8.02 (d, J=2.0 Hz, 1H);
.sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 14.4, 16.4, 23.0, 29.6,
29.7, 29.8, 29.9, 30.0, 31.5, 32.2, 36.3, 119.0 (q, J=320 Hz),
119.3, 126.6, 127.0, 127.5, 129.7, 129.9, 131.6, 131.8, 142.1,
125.9; IR (neat) .nu. 1427, 1213 cm.sup.-1 (--O--SO.sub.2--);
EI-MS, m/z=266 (M.sup.+); Anal. Calcd for C.sub.17H.sub.14OS: C,
76.66; H, 5.30%. Found: C, 76.97; H, 5.14%.
Synthesis Example 3
Synthesis of
3-methylthio-7-phenyl-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-72)
Synthesis Example 3-1
Synthesis of 3-methylthio-7-phenyl-2-naphthol
[0233] 3-Methylthio-7-phenyl-2-methoxynaphthalene (compound (4)-22)
synthesized in Example 16 was demethylated by the operation in
(Synthesis Example 1-1) to obtain
3-methylthio-7-phenyl-2-naphthol.
[0234] yield of 94%; yellow crystal (recrystallized with
hexane);
[0235] mp 149 to 150.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 2.44 (s, 3H), 6.64 (s, 1H), 7.38-7.40 (m, 2H), 7.48 (tt,
J=7.6, 1.8 Hz, 1H), 7.60 (d, J=8.5 Hz, 1H), 7.70-7.72 (m, 2H), 7.80
(dd, J=8.5, 2.0 Hz, 1H), 7.88 (s, 1H), 8.02 (d, J=2.0 Hz, 1H);
.sup.13C NMR (100 MHz, CDCl.sub.3) .delta. 20.2, 109.8, 124.1,
124.7, 127.7, 127.9, 128.5, 129.2 (.times.2), 134.1, 135.7, 140.1,
141.3, 153.4; IR (KBr) .nu. 3497 cm.sup.-1 (OH); EI-MS, m/z=266
(M.sup.+); Anal. Calcd for C.sub.17H.sub.14OS: C, 76.66; H, 5.30%.
Found: C, 76.97; H, 5.14%.
Synthesis Example 3-2
Synthesis of
3-methylthio-7-phenyl-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-72)
[0236] 3-Methylthio-7-phenyl-2-naphthol was
trifluoromethanesulfonylated by the same operation as that in
Synthesis Example 1-2 to obtain
3-methylthio-7-phenyl-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-72).
[0237] yield of 98%; yellow crystal (recrystallized with
hexane);
[0238] mp 87.8 to 88.7.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 2.62 (s, 3H), 7.41 (tt, J=7.2, 1.2 Hz, 1H),
7.45-7.52 (m, 2H), 7.68-7.71 (m, 2H), 7.72 (s, 1H), 7.79 (s, 1H),
7.82 (dd, J=8.4, 1.6 Hz, 1H), 7.87 (d, J=8.4 Hz, 1H), 8.00 (s, 1H);
.sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 16.0, 119.0 (q, J=321
Hz), 120.0, 125.9, 126.8, 127.6, 127.7, 127.8, 128.2, 129.3, 131.3,
131.7, 132.3, 139.8, 140.5, 146.0; IR (KBr) .nu. 1425, 1209
cm.sup.-1 (O--SO.sub.2--); EI-MS, m/z=398 (M.sup.+); Anal. Calcd
for C.sub.18H.sub.13O.sub.3S.sub.2F.sub.3: C, 54.26; H, 3.29%.
Found: C, 54.42; H, 3.08%.
Synthesis Example 4
Synthesis of
3-methylthio-6-phenyl-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-73)
Synthesis Example 4-1
Synthesis of 3-methylthio-6-phenyl-2-naphthol
[0239] The 3-methylthio-6-phenyl-2-methoxynaphthalene (compound
(4)-31) obtained in Example 17 was demethylated by the operation in
Synthesis Example 1-1 to obtain
3-methylthio-6-phenyl-2-naphthol.
[0240] yield of 73%; yellow crystal (recrystallized with
hexane);
[0241] mp 128.9 to 129.8.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 2.45 (s, 3H), 6.63 (s, 1H), 7.35 (s, 1H), 7.37
(tt, J=7.4, 1.3 Hz, 1H), 7.45-7.50 (m, 2H), 7.72 (dd, J=8.5, 1.8
Hz, 1H), 7.76 (d, J=8.6 Hz, 1H) 7.68-7.72 (m, 2H), 7.76 (d, J=8.5
Hz, 1H), 7.92 (d, J=1.8 Hz, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3)
.delta. 20.2, 109.4, 125.2, 125.5, 127.1, 127.3, 127.5, 127.6,
129.2, 129.5, 134.5 (.times.2), 137.0, 141.3, 153.1; IR (KBr) .nu.
3402 cm.sup.-1 (OH); EI-MS, m/z=266 (M.sup.+); Anal. Calcd for
C.sub.17H.sub.14OS: C, 76.66; H, 5.30%. Found: C, 76.50; H,
5.15%.
Synthesis Example 4-2
Synthesis of
3-methylthio-6-phenyl-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-73)
[0242] 3-Methylthio-6-phenyl-2-naphthol was
trifluoromethanesulfonylated by the same operation as that in
Synthesis Example 1-2 to obtain
3-methylthio-6-phenyl-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-73).
[0243] yield: quantitative; yellow crystal (recrystallized with
hexane);
[0244] mp 79.4 to 80.3.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 2.62 (s, 3H), 7.42 (tt, J=7.4, 1.3 Hz, 1H),
7.43-7.52 (m, 2H), 7.68-7.71 (m, 2H), 7.74 (s, 1H), 7.75 (s, 1H),
7.77 (dd, J=8.5, 1.8 Hz, 1H), 7.88 (d, J=8.5 Hz, 1H), 7.99 (d,
J=1.8 Hz, 1H); .sup.13C NMR (126 MHz, CDCl.sub.3) .delta. 16.0,
119.0 (q, J=321 Hz), 119.6, 124.9, 126.8, 127.1, 127.8, 128.2,
128.7, 129.3, 130.5, 131.9, 133.4, 140.7, 140.9, 145.6; IR (KBr)
.nu. 1429, 1225 cm.sup.-1 (O--SO.sub.2--); EI-MS, m/z=398
(M.sup.+); Anal. Calcd for C.sub.18H.sub.13O.sub.3S.sub.2F.sub.3:
C, 54.26; H, 3.29%. Found: C, 54.17; H, 3.01%.
Synthesis Example 5
Synthesis of
6-tolyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-83)
[0245] 6-Tolyl-3-methylthio-2-methoxynaphthalene (compound (4)-32,
10.5 g) obtained in Example 18 was demethylated with a
dichloromethane solution of BBr.sub.3 by the same method as that in
Synthesis Example 1-1, and subsequently
trifluoromethanesulfonylated to obtain
6-tolyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-83, 12.5 g, yield of 85%).
[0246] EI-MS, m/z=412 (M.sup.+)
Synthesis Example 6
Synthesis of
7-tolyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-82)
[0247] 7-Tolyl-3-methylthio-2-methoxynaphthalene (compound (4)-23,
15.4 g) obtained in Example 19 was demethylated with a
dichloromethane solution of BBr.sub.3 by the same method as that in
Synthesis Example 1-1, and subsequently
trifluoromethanesulfonylated to obtain
7-tolyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-82, 8.62 g, yield of 67%).
[0248] EI-MS, m/z=412 (M.sup.+)
Synthesis Example 7
Synthesis of
6-biphenyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-85)
[0249] 6-Biphenyl-3-methylthio-2-methoxynaphthalene obtained in
Example 20 (compound (4)-33, 15.4 g) was demethylated with a
dichloromethane solution of BBr.sub.3 by the same method as that in
(Synthesis Example 1-1), and subsequently
trifluoromethanesulfonylated to obtain
6-biphenyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-85, 15.9 g, yield of 77%).
[0250] EI-MS, m/z=474 (M.sup.+)
Synthesis Example 8
Synthesis of
7-biphenyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-84)
[0251] 7-Biphenyl-3-methylthio-2-methoxynaphthalene (compound
(4)-24, 15.8 g) obtained in Example 21 was demethylated with a
dichloromethane solution of BBr.sub.3 by the same method as that in
Synthesis Example 1-1, and subsequently
trifluoromethanesulfonylated to obtain
7-biphenyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-84, 18.9 g, yield of 93%).
[0252] EI-MS, m/z=474 (M.sup.+)
Synthesis Example 9
Synthesis of
7-butyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-74)
[0253] 7-Butyl-3-methylthio-2-methoxynaphthalene (compound (4)-04,
21.63 g, 83.1 mmol) obtained in Example 22 was demethylated with a
dichloromethane solution of BBr.sub.3 by the same method as that in
Synthesis Example 1-1, and subsequently
trifluoromethanesulfonylated to obtain
7-butyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-74, 18.5 g, yield of 59%).
[0254] EI-MS, m/z=378 (M.sup.+)
Synthesis Example 10
Synthesis of
7-hexyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-75)
[0255] 7-Hexyl-3-methylthio-2-methoxynaphthalene (compound (4)-08,
24.7 g) obtained in Example 23 was demethylated with a
dichloromethane solution of BBr.sub.3 by the same method as that in
(Synthesis Example 1-1), and subsequently
trifluoromethanesulfonylated to obtain
7-hexyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-75, 23.5 g, yield of 70%).
[0256] EI-MS, m/z=406 (M.sup.+)
Synthesis Example 11
Synthesis of
7-octyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-76)
[0257] 7-Octyl-3-methylthio-2-methoxynaphthalene (compound (4)-10,
27.09 g) obtained in Example 24 was demethylated with a
dichloromethane solution of BBr.sub.3 by the same method as that in
Synthesis Example 1-1, and subsequently
trifluoromethanesulfonylated to obtain
7-octyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-76, 25.00 g, yield of 64%).
[0258] EI-MS, m/z=434 (M.sup.+)
Synthesis Example 12
Synthesis of
7-dodecyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-78)
[0259] 7-Dodecyl-3-methylthio-2-methoxynaphthalene (compound
(4)-14, 34.1 g) obtained in Example 25 was demethylated with a
dichloromethane solution of BBr.sub.3 by the same method as that in
Synthesis Example 1-1, and subsequently
trifluoromethanesulfonylated to obtain
7-dodecyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-78, 33.7 g, yield of 72%).
[0260] EI-MS, m/z=490 (M.sup.+)
Synthesis Example 13
Synthesis of 1,2-bis(tributylstanyl)ethylene (compound (5)-05)
Synthesis Example 13-1
Synthesis of tributylstanylacetylene
##STR00025##
[0262] Under a nitrogen atmosphere, tributyltinchloride (8.6 ml, 32
mmol) was added to a THF (60 ml) solution of xylene of 18 w % Na
acetylene and a dispersion oil of a mineral oil (10 ml, 8.5 g, 32
mmol) at 0.degree. C. The solution was stirred at room temperature
for 17 hours. Then, the mixture was extracted with hexane, and
washed with saline water. The organic phases were mixed, and the
mixture was dried with MgSO.sub.4, and condensed. The condensed
product was distilled at reduced pressure (85 to 120.degree. C.,
approximately 0.7 mmHg) to obtain tributylstanylacetylene (3.6 g,
34%) as a colorless oily substance.
[0263] .sup.1H-NMR (400 MHz, CDCl.sub.3) .delta. 0.91 (t, 9H, J=8.0
Hz), 1.02 (t, 8H, J=8.0 Hz), 1.35 (sextet, 6H, J=8.0 Hz), 1.58
(quintet, 6H, J=8.0 Hz), 2.20 (s, 1H)
Synthesis Example 13-2
Synthesis of 1,2-bis(tributylstanyl)ethylene (compound (5)-05)
##STR00026##
[0265] Under a nitrogen atmosphere, azobisisobutyronitrile (100 mg,
0.60 mmol) was added to a toluene (20 ml) solution of
tributylstanylacetylene (1.6 g, 5 mmol) and tributyltinhydride (1.3
ml, 5 mmol). The mixture was heated and stirred for 17 hours at
90.degree. C. Water (20 ml) was added, and the mixture was
condensed. The mixture was extracted with hexane. The extracted
solution was washed with saline water to obtain
1,2-bis(tributylstanyl)ethylene (compound (5)-05) (3.0 g, 90%) as a
colorless oily substance.
[0266] .sup.1H-NMR (400 MHz, CDCl.sub.3) .delta. 0.86-0.91
(multiplet, 15H), 1.31 (sextet, 6H, J=8.0 Hz), 1.50 (quintet, 6H,
J=8.0 Hz), 6.88 (s, 2H)
Example 26
Synthesis of
trans-1,2-bis(6-decyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-64)
##STR00027##
[0268] Pd(PPh.sub.3).sub.4 (322 mg, 0.29 mmol, 7 mol %) was added
to a DMF (40 ml) solution of
6-decyl-3-methylthio-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-81) (1.9 g, 4.1 mmol) and
1,2-bis(tributylstanyl)ethylene (compound (5)-05). The mixture was
heated and stirred at 90.degree. C. for 17 hours in a dark place,
diluted with water, and extracted with chloroform. The extracted
solution was dried with MgSO.sub.4, and condensed. The residue was
refined by column chromatography (silica gel, developed with
dichloromethane) to obtain
trans-1,2-bis(6-decyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-64) (2.3 g, quantitative) as a yellow solid.
[0269] mp 116.8 to 117.7.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 0.88 (t, J=6.4 Hz, 6H), 1.29-1.70 (m, 32H),
2.58 (s, 6H), 2.75 (t, J=8.4 Hz, 4H), 7.29 (dd, J=8.8, 1.6 Hz, 2H),
7.52 (s, 2H), 7.59 (s, 2H), 7.64 (s, 2H), 7.76 (d, J=8.4 Hz, 2H),
8.06 (s, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3) .delta. 14.4,
16.8, 23.0, 24.2, 29.6, 29.8, 29.9, 30.0, 31.7, 32.2, 36.5, 124.3,
125.2, 125.3, 127.6, 128.0, 128.4, 130.3, 133.9, 134.5, 136.0,
141.6; EI-MS m/z=652 (M.sup.+).
Example 27
Synthesis of
trans-1,2-bis(7-decyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-12)
[0270] Trans-1,2-bis(7-decyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-12) was obtained from
7-decyl-3-methylthio-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-77) and 1,2-bis(tributylstanyl)ethylene (compound
(5)-05) by the same operation as that in Example 26. yield of 98%;
yellow crystal (recrystallized with hexane);
[0271] mp 87.8-88.7.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 2.62 (s, 3H), 7.41 (tt, J=7.2, 1.2 Hz, 1H), 7.45-7.52 (m,
2H), 7.68-7.71 (m, 2H), 7.72 (s, 1H), 7.79 (s, 1H), 7.82 (dd,
J=8.4, 1.6 Hz, 1H), 7.87 (d, J=8.4 Hz, 1H), 8.00 (s, 1H); EI-MS,
m/z=398 (M.sup.+); Anal. Calcd for
C.sub.18H.sub.13O.sub.3S.sub.2F.sub.3: C, 54.26; H, 3.29%. Found:
C, 54.42; H, 3.08%.
Example 28
Synthesis of
trans-1,2-bis(3-methylthio-7-phenylnaphtho-2-yl)ethylene (compound
(6)-22)
[0272] Trans-1,2-bis(3-methylthio-7-phenylnaphtho-2-yl)ethylene
(compound (6)-22) was obtained from
3-methylthio-7-phenyl-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-72) and 1,2-bis(tributylstanyl)ethylene (compound
(5)-05) by the same operation as that in Example 26.
[0273] yield of 63%; yellow solid (recrystallized with hexane);
[0274] mp 87.8 to 88.7.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 2.63 (s, 6H), 7.40 (tt, J=7.4, 1.2 Hz, 2H),
7.48-7.52 (m, 4H), 7.68 (s, 2H), 7.73-7.76 (m, 4H), 7.72 (s, 2H),
7.72 (d, J=8.2 Hz, 2H), 7.83 (d, J=8.2 Hz, 2H), 8.08 (s, 2H), 8.17
(s, 2H); EI-MS, m/z=524 (M.sup.+); Anal. Calcd for
C.sub.34H.sub.25S.sub.2: C, 82.40; H, 5.38%. Found: C, 82.38; H,
5.22%.
Example 29
Synthesis of
trans-1,2-bis(3-methylthio-6-phenylnaphtho-2-yl)ethylene (compound
(6)-31)
[0275] Trans-1,2-bis(3-methylthio-6-phenylnaphtho-2-yl)ethylene
(compound (6)-31) was obtained from
3-methylthio-6-phenyl-2-(trifluoromethanesulfonyloxy)naphthalene
(compound (4)-73) and 1,2-bis(tributylstanyl)ethylene (compound
(5)-05) by the same operation as that in Example 26.
[0276] yield of 57%; yellow solid (recrystallized with hexane);
[0277] mp 191.5 to 192.4.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 2.64 (s, 6H), 7.40 (tt, J=7.2, 1.6 Hz, 2H),
7.48-7.53 (m, 4H), 7.71 (s, 2H), 7.72 (s, 2H), 7.73-7.76 (m, 4H),
7.76 (d, J=8.7 Hz, 2H), 7.94 (d, J=8.7 Hz, 2H), 7.97 (s, 2H), 8.14
(s, 2H); EI-MS, m/z=524 (M.sup.+); Anal. Calcd for
C.sub.34H.sub.25S.sub.2: C, 82.40; H, 5.38%. Found: C, 82.22; H,
5.29%.
Example 30
Synthesis of
trans-1,2-bis(6-tolyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-32)
[0278] Trans-1,2-bis(6-tolyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-32, 2.0 g, yield of 24%) as a light yellow solid was
obtained from
6-tolyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-83, 12.5 g) by the same operation as that in Example
26.
[0279] EI-MS, m/z=552 (M.sup.+)
Example 31
Synthesis of
trans-1,2-bis(7-tolyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-23)
[0280] Trans-1,2-bis(7-tolyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-23, 3.64 g, yield of 64%) as a light yellow solid was
obtained from
7-tolyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-82, 8.50 g) by the same operation as that in Example
26.
[0281] EI-MS, m/z=552 (M.sup.+)
Example 32
Synthesis of
trans-1,2-bis(6-biphenyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-33)
[0282]
Trans-1,2-bis(6-biphenyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-33, 8.52 g, yield of 76%) as a light yellow solid was
obtained from
6-biphenyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-85, 15.8 g) by the same operation as that in Example
26.
[0283] EI-MS, m/z=676 (M.sup.+)
Example 33
Synthesis of
trans-1,2-bis(7-biphenyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-24)
[0284]
Trans-1,2-bis(7-biphenyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-24, 11.56 g, yield of 86%) as a light yellow solid
was obtained from
7-biphenyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-84, 18.9 g) by the same operation as that in Example
26.
[0285] EI-MS, m/z=676 (M.sup.+)
Example 34
Synthesis of
trans-1,2-bis(7-butyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-04)
[0286] Trans-1,2-bis(7-butyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-04) as a light yellow solid (5.32 g, yield of 45%)
was obtained from
7-butyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-74, 18.20 g, 47.6 mmol) by the same operation as that
in Example 26.
[0287] EI-MS, m/z=492 (M.sup.+)
Example 35
Synthesis of
trans-1,2-bis(7-hexyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-08)
[0288] Trans-1,2-bis(7-hexyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-08) as a light yellow solid (6.73 g, yield of 43%)
was obtained from
7-hexyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-75, 23.3 g) by the same operation as that in Example
26.
[0289] EI-MS, m/z=540 (M.sup.+)
Example 36
Synthesis of
trans-1,2-bis(7-octyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-10)
[0290] Trans-1,2-bis(7-octyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-10) as a light yellow solid (7.46 g, yield of 43%)
was obtained from
7-octyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-76, 25.00 g) by the same operation as that in Example
26.
[0291] EI-MS, m/z=596 (M.sup.+)
Example 37
Synthesis of
trans-1,2-bis(7-dodecyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-14)
[0292] Trans-1,2-bis(7-dodecyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-14) as a light yellow solid (8.08 g, yield of 40%)
was obtained from
7-octyl-3-methylthio-2-trifluoromethanesulfonyloxynaphthalene
(compound (4)-78, 27.8 g) by the same operation as that in Example
26.
[0293] EI-MS, m/z=709 (M.sup.+)
Synthesis Example 14
Synthesis of
2,9-didecyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene (compound
(2)-64)
##STR00028##
[0295] A chloroform (4 ml) solution of
trans-1,2-bis(6-decyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-64) (38 mg, 58 mmol) and I.sub.2 (470 mg, 1.8 mmol)
was stirred at room temperature for 20 hours. The mixture was
condensed, and methanol (5 ml) and a NaHSO.sub.3 aqueous solution
(5 ml) were added to the mixture. The mixture was filtered, and
washed with water, acetone, methanol, and toluene to obtain
2,9-didecyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene (compound
(2)-64) (29 mg, 81%) as a yellow solid.
[0296] EIMS (70 eV) m/z=620 (M.sup.+).
Example 38
Synthesis of 3,10-didecyl
dinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene (compound
(1)-12)
[0297] 3,10-Didecyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-12) was obtained from
trans-1,2-bis(7-decyl-3-methylthionaphthalene-2-yl)ethylene
(compound (6)-12) by the same method as that in Synthesis Example
14.
[0298] yield of 71%; mp 187 to 188.degree. C.;
[0299] .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 0.88 (t, J=6.9 Hz,
6H), 1.24-1.79 (m, 32H), 2.82 (t, J=7.7 Hz, 4H), 7.38 (dd, J=8.5,
1.6 Hz, 2H), 7.79 (s, 2H), 7.86 (d, J=8.5 Hz, 2H), 8.29 (s, 2H),
8.36 (s, 2H); EI-MS, m/z=620 (M.sup.+); Anal. Calcd for
C.sub.42H.sub.52S.sub.2: C, 81.46; H, 8.43%. Found: C, 81.13; H,
8.43%.
Example 39
Synthesis of 3,10-diphenyl
dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (3,10-PhDNTT)
(compound (1)-22)
[0300] 3,10-Diphenyldinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene
(3,10-PhDNTT) (compound (1)-22) was obtained from
trans-1,2-bis(3-methylthio-7-phenylnaphtho-2-yl)ethylene (compound
(6)-22) by the same method as that in Synthesis Example 14. yield
of 85%; mp>300.degree. C.;
[0301] EI-MS, m/z=492 (M.sup.+); Anal. Calcd for
C.sub.34H.sub.20S.sub.2: C, 82.89; H, 4.09%. Found: C, 82.80; H,
3.78%.
Example 40
Synthesis of 2,9-diphenyl
dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (2,9-PhDNTT)
(compound (1)-31)
[0302]
2,9-Diphenyldinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene(2,9-PhDN-
TT) (compound (1)-31) was obtained from
trans-1,2-bis(3-methylthio-6-phenylnaphtho-2-yl)ethylene (compound
(6)-31) by the same method as that in Synthesis Example 14.
[0303] yield of 89%; mp>300.degree. C.;
[0304] EI-MS, m/z=492 (M.sup.+); Anal. Calcd for
C.sub.34H.sub.20S.sub.2: C, 82.89; H, 4.09%. Found: C, 82.73; H,
3.75%.
Example 41
Synthesis of
2,9-ditolyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene (compound
(1)-32)
[0305] 2,9-Ditolyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-32) as a yellow solid (1.78 g, 95%) was obtained from
trans-1,2-bis(6-tolyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-32, 2.0 g) by the same method as that in Synthesis
Example 14.
[0306] EI-MS, m/z=520 (M.sup.+), 427, 260 (M+/2).
[0307] thermal analysis (endothermic peak): 492.degree. C. (TG-DTA
was used, nitrogen)
Example 42
Synthesis of
3,10-ditolyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-23)
[0308] 3,10-Ditolyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-23) as a yellow solid (3.38 g, quantitative) was
obtained from
trans-1,2-bis(7-tolyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-23, 3.60 g) by the same method as that in Synthesis
Example 14.
[0309] EI-MS, m/z=520 (M.sup.+), 427, 260 (M+/2), 172.
[0310] thermal analysis (endothermic peak): 401.degree. C. (TG-DTA
was used, nitrogen)
Example 43
Synthesis of
2,9-dibiphenyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-33)
[0311]
Trans-1,2-bis(6-biphenyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-33, 8.40 g) was reacted with iodine by the same
method as that in Synthesis Example 14 to obtain
2,9-dibiphenyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-33) as a yellow solid (7.76 g, 97%).
[0312] EI-MS, m/z=644 (M.sup.+), 566, 490, 429, 322 (M+/2),
207.
[0313] thermal analysis (endothermic peak), no clear peak at less
than 500.degree. C. (TG-DTA was used, nitrogen)
Example 44
Synthesis of
3,10-dibiphenyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-24)
[0314]
Trans-1,2-bis(7-biphenyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-24, 11.50 g) was reacted with iodine by the same
method as that in Synthesis Example 14 to obtain
3,10-dibiphenyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-24) as a yellow solid (10.32 g, yield of 94%).
[0315] EI-MS, m/z=644 (M.sup.+), 492, 429, 322 (M+/2), 270.
[0316] thermal analysis (endothermic peak), no clear peak at less
than 500.degree. C. (TG-DTA was used, nitrogen)
Example 45
Synthesis of
3,10-dibutyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-04)
[0317] Trans-1,2-bis(7-butyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-04) was reacted with iodine by the same method as
that in Synthesis Example 14 to obtain
3,10-dibutyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-04) as a yellow solid (4.66 g, quantitative).
[0318] EI-MS, m/z=452 (M.sup.+), 409, 366, 184, 183.
[0319] thermal analysis (endothermic peak): 185, 283.degree. C.
(DSC was used, nitrogen)
[0320] .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 0.98 (t, 6H),
.delta. 1.35.about.1.50 (m, 4H), .delta. 1.70-1.80 (m, 4H), .delta.
2.80-2.90 (m, 4H) .delta. 7.39 (dd, 2H, ArH) .delta. 7.78 (s, 2H,
ArH) .delta. 7.84 (d, 2H, ArH) .delta. 8.27 (s, 2H, ArH) .delta.
8.34 (s, 2H, ArH).
Example 46
Synthesis of
3,10-dihexyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-08)
[0321] Trans-1,2-bis(7-hexyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-08, 6.50 g) was reacted with iodine by the same
method as that in Synthesis Example 14 to obtain
3,10-dihexyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-08) as a yellow solid (3.18 g, yield of 52%).
[0322] EI-MS, m/z=508 (M.sup.+), 437, 366, 184, 183
[0323] thermal analysis (endothermic peak): 202, 259.degree. C.
(DSC was used, nitrogen)
[0324] .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 0.90 (t, 6H),
.delta. 1.20.about.1.55 (m, 12H), .delta. 1.70-1.80 (m, 4H),
.delta. 2.75-2.90 (m, 4H) .delta. 7.39 (dd, 2H, ArH) .delta. 7.78
(s, 2H, ArH) .delta. 7.84 (d, 2H, ArH) .delta. 8.27 (s, 2H, ArH)
.delta. 8.34 (s, 2H, ArH).
Example 47
Synthesis of
3,10-dioctyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-10)
[0325] Trans-1,2-bis(7-hexyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-10, 7.20 g, 12.1 mmol) was reacted with iodine by the
same method as that in Synthesis Example 14 to obtain
3,10-dioctyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-10) as a yellow solid (3.50 g, yield of 51%).
[0326] EI-MS, m/z=564 (M.sup.+), 465, 366, 184, 183
[0327] thermal analysis (endothermic peak): 177, 237.degree. C.
(DSC was used, nitrogen) .sup.1H NMR (400 MHz, CDCl.sub.3) .delta.
0.88 (m, 6H), .delta. 1.10.about.1.50 (m, 20H), .delta. 1.60-1.85
(m, 4H), .delta. 2.70-2.90 (m, 4H) .delta. 7.36 (m, 2H, ArH)
.delta. 7.77 (s, 2H, ArH) .delta. 7.83 (d, 2H, ArH) .delta. 8.26
(s, 2H, ArH) .delta. 8.30 (s, 2H, ArH).
Example 48
Synthesis of
3,10-didodecyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-14)
[0328] Trans-1,2-bis(7-dodecyl-3-methylthionaphthalen-2-yl)ethylene
(compound (6)-14, 7.80, 11 mmol) was reacted with iodine by the
same method as that in Synthesis Example 14 to obtain
3,10-didodecyldinaphtho[2,3-b:2',3'-f]thieno[2,3-b]thiophene
(compound (1)-14) as a yellow solid (6.26 g, yield of 84%).
[0329] EI-MS, m/z=677 (M.sup.+), 521, 366, 184, 183
[0330] thermal analysis (endothermic peak): 100, 123, 158,
212.degree. C. (DSC was used, nitrogen)
[0331] .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 0.80-0.90 (m, 6H),
.delta. 1.20.about.1.60 (m, 36H), .delta. 1.70-1.85 (m, 4H),
.delta. 2.80-2.90 (m, 4H) .delta. 7.36 (dd, 2H, ArH) .delta. 7.80
(s, 2H, ArH) .delta. 7.83 (d, 2H, ArH) .delta. 8.26 (s, 2H, ArH)
.delta. 8.34 (s, 2H, ArH).
[0332] As above, development of the novel synthesis method enabled
synthesis of a variety of DNTT derivatives (1) and (2) that are
extremely high performance organic semiconductors having a
substituent at various positions. Particularly, synthesis method of
the present invention succeeded for the first time in synthesis of
the compound (1) exhibiting excellent properties as the
semiconductor.
[0333] Next, a novel heterocyclic compound represented by the
compound (1) and a field effect transistor having a semiconductor
layer comprising the compound, and a field effect transistor having
a semiconductor layer comprising the compound (2) synthesized in
the present invention will be specifically described.
Example 49
Creation of Top Contact Type Field Effect Transistor
[0334] An n-doped silicon wafer subjected to an
octadecyltrichlorosilane treatment and having a 300 nm SiO.sub.2
thermal oxide film (surface resistance of 0.02.OMEGA.cm or less)
was placed inside of a vacuum deposition apparatus, and the air in
the apparatus was discharged until the degree of vacuum of the air
reached 5.0.times.10.sup.-3 Pa or less. Each of the compounds
(1)-12, (1)-22, and (1)-31 was deposited onto an electrode to have
a thickness of 50 nm by a resistance heating deposition method
under the condition of a substrate temperature of approximately
60.degree. C. Thereby, a semiconductor layer (2) was formed. Next,
a shadow mask for creating an electrode was attached to this
substrate. The substrate was placed inside of the vacuum deposition
apparatus, and the air in the apparatus was discharged until the
degree of vacuum of the air reached 1.0.times.10.sup.-4 Pa or less.
The gold electrodes, that is, the source electrode (1) and the
drain electrode (3) were deposited by the resistance heating
deposition method to have a thickness of 40 nm. Thereby, a TC (top
contact) type field effect transistor of the present invention was
obtained.
[0335] In the field effect transistor, the thermal oxide film in
the n-doped silicon wafer having a thermal oxide film has the
function of the insulator layer (4), and the n-doped silicon wafer
has the functions of the substrate (6) and the gate electrode (5)
(see FIG. 3).
[0336] The obtained field effect transistor was placed inside of a
prober, and the semiconductor properties were measured using a
semiconductor parameter analyzer 4155C (manufactured by Agilent
Technologies, Inc.). For the semiconductor properties, the drain
current-drain voltage was measured by scanning the gate voltage
from 10 V to -100 V at 20 V steps, and scanning the drain voltage
from 10 V to -100 V. Current saturation was observed. The obtained
voltage current curve indicated that the element is a p type
semiconductor. The calculated carrier mobility is shown in Table
7.
Comparative Example 1
[0337] Instead of the compound according to the present embodiment
used in Example 49, DNTT (Ref-01), 3,10-DM-DNTT (Ref-02; a compound
wherein R.sup.1 in (1) was a methyl group), and 2,9-DM-DNTT
(Ref-03; a compound wherein R.sup.2 in (1) was a methyl group) were
used, and TC type field effect transistors were obtained by the
same operation as that in Example 49. The compounds used and the
results are shown in Table 7.
##STR00029##
TABLE-US-00007 TABLE 7 Compound No. R.sup.1 R.sup.2 Mobility
(cm.sup.2/Vs) (1)-12 n-C.sub.10H.sub.21 8.0 (1)-22 Ph 3.4 (1)-31 Ph
3.9 Ref-01 3.0 Ref-02 Me 0.2 Ref-03 Me 0.2
[0338] Ref-02 and Ref-03, that is, the DNTT having a short alkyl
chain exhibited only the properties not more than those of the DNTT
scaffold (Ref-01). In the case where the compound (1) of the
present invention was used to create a field effect transistor,
however, the properties of the field effect transistor were
extremely high as a field effect transistor formed by the
deposition method using a standard organic substance as the
semiconductor. The mobility of the field effect transistor was
equal to that of the field effect transistor formed using a single
crystal that is hardly realized in industrial scale. Such extremely
high mobility was obtained by the vacuum evaporation method
industrially suitable. The field effect transistor of this
application having high performance extremely increased the
industrial value, for example, extended the range of usable
applications.
Example 50
[0339] Using the compounds of this application synthesized in
Examples 38 to 48, and the compound Ref-01 in Comparative Example
1, and the compound (2)-64, TC type field effect transistors were
created by the same operation as that in Example 49 except that a
substrate treated with HMDS-SAM was used, the substrate temperature
during deposition was 25.degree. C. and 100.degree. C., L=50 .mu.m,
and W=2000 .mu.m. The semiconductor properties of the obtained
transistors were measured according to Example 49. The calculated
carrier mobility is shown in Table 8. These results show that the
compound of this application exhibits high performance as a p type
semiconductor material.
TABLE-US-00008 TABLE 8 Compound No. R.sup.1 R.sup.2 Mobility
(cm.sup.2/Vs) (1)-04 n-Bu 3.16 (1)-08 n-C.sub.6H.sub.13 2.96 (1)-10
n-C.sub.8H.sub.17 3.22 (1)-12 n-C.sub.10H.sub.21 3.98 (1)-14
n-C.sub.12H.sub.25 3.78 (1)-22 Ph 4.04 (1)-23 4-Tolyl 1.78 (1)-31
Ph 2.06 (1)-32 4-Tolyl 2.09 (1)-33 PhPh 1.86* Ref-01 1.22
Example 51
[0340] Using the compound (1)-22 synthesized in Example 39 and the
compound (2)-64 synthesized in Synthesis Example 14, TC type field
effect transistors were created by the same operation as that in
Example 49 except that a substrate treated with HMDS-SAM was used,
the substrate temperature during deposition was 100.degree. C.,
L=40 .mu.m, and W=1500 .mu.m. The obtained field effect transistors
were subjected to a heat resistance test. The measurement results
are shown in Table 9. Comparing the initial properties (.mu.=1.66
cm.sup.2/Vs, Vth=-14 V, Ion/off.about.10.sup.9), the mobility was
approximately 1.6 cm.sup.2/Vs even after annealing at 100.degree.
C. and 150.degree. C., and the values of these properties were kept
approximately equal to the initial values thereof. The properties
were improved, for example, Vth was shifted to a low potential
side. In contrast, the mobility of the compound (2)-64 reduced by
half at approximately 120.degree. C. From these experiments, it was
found out that the compound having an aryl group to be substituted
such as the compound (1)-22 of the present invention has high
thermal stability, and can attain a transistor that can stand
industrial processes.
TABLE-US-00009 TABLE 9 Compound No. (1)-22 (2)-64 .mu./cm.sup.2/
V.sub.th/ I.sub.on/ .mu./cm.sup.2/ V.sub.th/ I.sub.on/ Vs V
I.sub.off Vs V I.sub.off Not annealed 1.66 -14.0 1.0 .times.
10.sup.9 1.96 0.2 1.0 .times. 10.sup.9 Annealed 1.59 -8.8 1.0
.times. 10.sup.9 1.52 -1.0 1.0 .times. 10.sup.9 (100.degree. C.)
Annealed 1.62 -7.0 1.0 .times. 10.sup.9 0.77 0.8 1.0 .times.
10.sup.9 (150.degree. C.)
Example 52
[0341] Absorption spectrums of saturated solutions obtained by
dissolving the DNTT having a C10 alkyl group at 2,9-positions
(compound (2)-64), the DNTT having a C10 alkyl group at
3,10-positions (compound (1)-12), and the like in chloroform are
shown in FIG. 4. In the case of the DNTT having a C10 long-chain
alkyl group, from the results, the relative intensity of the
longest absorption wavelength according to the substitution
position was 3.9 in 3,10-C10-DNTT (compound (1)-12) wherein the
relative intensity was 1 in 2,9-C10-DNTT (compound (2)-64). It was
found out that 3,10-C10-DNTT (compound (1)-12) exhibited high
solubility because of the difference in the substitution position.
The solubility at 60.degree. C. in toluene was 45 mg/L in
2,9-C10-DNTT (compound (2)-64) and >260 mg/L in 3,10-C10-DNTT
(compound (1)-09). It was clearly found out that the solubility of
3,10-C10-DNTT (compound (1)-12) was also high in a heating state
(Table 10).
TABLE-US-00010 TABLE 10 Solubility ratio Solubility Compound No.
R.sup.1 R.sup.2 Chloroform 60.degree. C. toluene (1)-12
n-C.sub.10H.sub.21 3.8 >260 mg/L (2)-64 n-C.sub.10H.sub.21 1 45
mg/L
[0342] From FIG. 4 wherein the solubility of the DNTT was 1, the
solubility ratio of the DNTT having a short alkyl chain Ref-02 was
0.1 and the solubility ratio of the DNTT having a short alkyl chain
Ref-03 was 0.5. Ref-02 and Ref-03 do not dissolve in most of
solvents as the DNTT scaffold (Ref-01, the compound does not
dissolve in most of solvents). It was found out that the compound
(1)-12 having an alkyl substituent at 3,10-positions has higher
solvent solubility than that of the compound (2)-64 having an alkyl
substituent at 2,9-positions. It was also found out that
considering the solution process, the compound having an alkyl
substituent at 3,10-positions has more excellent properties.
Namely, use of such high solubility enables production of a field
effect transistor by creating a practical ink for creating a
semiconductor device or applying the ink created.
Example 53
[0343] An n-doped silicon wafer subjected to an
octadecyltrichlorosilane treatment and having a 300 nm SiO.sub.2
thermal oxide film (surface resistance of 0.02.OMEGA.cm or less)
was placed inside of a vacuum deposition apparatus, and the air in
the apparatus was discharged until the degree of vacuum reached
5.0.times.10.sup.-3 Pa or less. Each of the compounds (1)-12 and
2-(64) was deposited onto an electrode to have a thickness of 50 nm
by the resistance heating deposition method under the condition of
the substrate temperature of approximately 100.degree. C. Thereby,
a semiconductor layer (2) was formed. Next, a shadow mask for
creating an electrode (channel width of 1500 .mu.m) having a
channel length L of 40 .mu.m or 190 .mu.m was attached to this
substrate. The substrate was placed inside of the vacuum deposition
apparatus, and the air in the apparatus was discharged until the
degree of vacuum reached 1.0.times.10.sup.-4 Pa or less. The gold
electrodes, namely, the source electrode (1) and the drain
electrode (3) were deposited by the resistance heating deposition
method to have a thickness of 40 nm. Thereby, a TC (top contact)
type field effect transistor of the present invention was obtained.
The results obtained by measuring these semiconductor properties in
the same manner as in Example 49 are shown in Table 11. The results
show that in the compound (1)-12 having a substituent at
3,10-positions, the mobility hardly reduced at L=40 .mu.m and L=190
.mu.m, and channel length dependency was small. Meanwhile, the
compound (2)-64 having a substituent at 2,9-positions attained a
transistor having the mobility 6.1 cm.sup.2/Vs at L=190 .mu.m, but
the channel length dependency was remarkable. At L=40 .mu.m, the
mobility reduced by half or less.
TABLE-US-00011 TABLE 11 Compound L (cm.sup.2/ Vth Ion/ No. R.sup.1
R.sup.2 (cm) Vs) (V) off (2)-64 n-C.sub.10H.sub.21 40 3.7 -10
10.sup.8 (2)-64 n-C.sub.10H.sub.21 190 6.1 -5 10.sup.9 (1)-12
n-C.sub.10H.sub.21 40 3.15 -19 10.sup.9 (1)-12 n-C.sub.10H.sub.21
190 3.56 -17 10.sup.8
[0344] It is assumed that a shorter channel is demanded in creation
of devices, and reduction in properties such as mobility needs to
be prevented in such cases. The results indicated that use of the
DNTT having a substituent at 3,10 positions and having small
channel length dependency enables production of a field effect
transistor that can stand practical use in devices.
[0345] As above, it revealed that the compound (DNTT having an
alkyl substituent at 3,10-positions) wherein R.sup.1 in the
compound (1) of the present invention each independently represents
a C2-C16 alkyl group and R.sup.2 is a hydrogen atom has improved
solubility compared to that of the DNTT having an alkyl substituent
at 2,9-positions. It turned out that when at least one of R.sup.1
and R.sup.2 is an aryl group, heat resistance significantly
improves compared to the DNTT in which the at least one of R.sup.1
and R.sup.2 is not substituted, and the properties as the organic
semiconductor significantly improve. Thus, the present invention
can attain an organic field effect transistor having excellent
properties, and create an element exhibiting carrier mobility
suitable for practical use. It revealed that the present invention
has high industrial values such as adaptability to various device
creation processes and extension of usable processes and
applications areas.
REFERENCE SIGNS LIST
[0346] Same referential numerals are given to same elements in FIG.
1 to FIG. 3. [0347] 1 Source electrode [0348] 2 Semiconductor layer
[0349] 3 Drain electrode [0350] 4 Insulator layer [0351] 5 Gate
electrode [0352] 6 Substrate [0353] 7 Protective layer
* * * * *